Organophosphorus Chemistry
Volume 23
A Specialist Periodical Report
Organophosphorus Chemistry Volume 23 A Review o...
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Organophosphorus Chemistry
Volume 23
A Specialist Periodical Report
Organophosphorus Chemistry Volume 23 A Review of the Recent Literature Published between July 1990 and June 1991 Senior Reporters
D. W. Allen, Sheffield Hallam University B. J. Walker, The Queen's University of Belfast Reporters
C. W. Allen, University of Vermont, U.S.A. R. Cosstick, University of Liverpool 0. Dahl, University of Copenhagen, Denmark R. S. Edmundson, formerly of University of Bradford C. D.Hall, King's College, London
SOCIETY OF CHEMISTRY
ISBN 0-85186-216-0 ISSN 0306-0713 Copyright 0The Royal Society of Chemistry 1992 All Rights Reserved N o part of this book may be reproduced or transmitted in any form or by any means -graphic, electronic, including photocopying, recording, taping, or information storage and retrieval systems - without written permission from The Royal Society of Chemistry Published by The Royal Society of Chemistry, Thomas Graham House, The Science Park, Cambridge CB4 4WF
Printed in Great Britain by Bookcraft (Bath) Ltd.
In trod uction
The "Physical Methods" chapter has not appeared in Organophosphorus Chemistry since volume 19 and our difficulty in finding an author to replace John Tebby is a measure of the wide knowledge and volume of work required. We are delighted that Declan Gilheany from University College, Dublin has now agreed to take on the task from volume 24 and, in his first contribution, to cover the major points from the appropriate literature of the last few years. Interest in the synthesis and chemistry of phosphines and phosphonium salts continues at a high level. Reports include one describing a sterically protected triarylphosphine which survives heating in peracetic acid for 24 hours! Compounds containing p,-bonded phosphorus continue to be the subject of major interest. The phospha-alkyne ClCP has been characterised and it has been shown that simple phospha-alkynes RCP, including that with R=H, can persist in solution for several days. Further evidence is available that, for p,-bonded compounds, the structural effects of hybridisation changes at phosphorus are much more significant than for nitrogen; x - b o n d ing interactions may account for only half of the observed bond shortening. There have been relatively few truly novel developments in pentaand hexaco-ordinated phosphorus compounds. The emphasis continues to be on cyclic phosphoranes and structural aspects of pentaco-ordinated compounds and a useful review covering X-ray and 1H n.m.r. investigations of the latter area has appeared. It has been shown that phosphoranes containing five-, six-, and seven-membered rings retain their solid state structures in solution and that the boat conformation is preferred for saturated six-membered rings in apical-equatorial orientations of trigonal bipyramids. T h e importance of apical-equatorial ring orientations for intermediates in enzymatic reactions of phosphorinanes appearing as tbp cyclic AMP analogues has been emphasised. New developments in phosphine oxide chemistry have been largely confined to the continuing use of stabilised carbanions in synthesis. In view of this we intend to stop covering the area in a separate chapter from Volume 25. With the exception of the phosphine oxide-stabilised carbanion chemistry, which will be reported in "Ylides and Related Compounds", the material now covered in the chapter will be incorporated in chapter 1 together with phosphines and phosphonium salts. V
vi
Introduction
With the notable exception of nucleotide chemistry, highlights in the trivalent- and pentavalent-phosphorus acid areas have not been numerous in the period covered. Olah's demonstration that triisopropyl phosphite can be used as a substitute for Clemmenson/Wolf-Kishner techniques for the reduction of ketones to hydrocarbons is noteworthy, as is the remarkable structure of P 2 S e 5 . As noted in the Introduction to Volume 22, the pentavalent phosphorus acid area remains to a large extent in the doldrums. T h e exceptions to this are in the myo-inositol phosphate and aminophosphonic acid areas, with a rapidly growing interest in the synthesis of peptide-like compounds based on the latter. There has been substantially more activity in phosphonic/phosphinic acid chemistry than in that of phosphoric acids. Hammerschmidt's work on the biosynthesis of natural products having the P-C link, e.g. the role of hydroxyalkylphosphonic acids in fosfomycin and also the biosynthetic pathways to 2-aminoethylphosphonic acid, is worthy of special mention. Nucleotide chemistry continues to be dominated by the potential use of analogues as chemotherapeutic agents, particularly as anti-HIV drugs. In spite of many problems the anti-sense approach to viral chemotherapy continues to make steady progress and it is likely that anti-viral oligodeoxynucleotides will enter phase-one clinical trials in the near future. Interest in the interaction of nucleic acids with many diverse ligands which bind and cleave DNA has been maintained by the world-wide initiatives in molecular recognition and numerous elegant studies have appeared on this subject. Reports of theoretical and, especially, mechanistic studies on ylides and phosphonate-stabilised carbanions and their reactions are much reduced this year although these reactions continue to be very extensively used in synthesis. Developments include the increased range of heterocyclic systems synthesised by aza-Wittig reactions, the increased number and complexity of phosphonates used in natural product synthesis and the variety of new methods of introducing fluorinated-alkyl functions. Activity continues to increase in both basic and applied areas of phosphazene chemistry. Exciting advances in (po1y)phosphazene chemistry include anionic initiation of condensation polymerisation of phosphoranamines at modest temperatures, new heterophosphazene polymers and the first interpenetrating network polymer containing a poly(ph0sphazene) hydrogel which can encapsulate living cells while allowing them to retain biological activity. Finally, an overview of the regio- and stereochemical pathways followed in the reactions of cyclophosphazenes and principles for predicting these pathways has become available.
D W Allen and B J Walker
Contents
CHAPTER
1
Phosphines and Phosphonium S a l t s By D.W. Allen
1
Introduction
1
2
Phosphines
1
2.1 Preparation
1
From Halogenophosphines and Organometallic Reagents Preparation of Phosphines from Metallated Phosphines Preparation of Phosphines by Addition of P-H to Unsaturated Compounds Preparation of Phosphines by Reduction Miscellaneous Methods of Preparing Phosphines
2.1.1 2.1.2 2.1.3 2.1.4
2.1.5
2.2 Reactions of Phosphines 2.2.1 2.2.2 2.2.3 2.2.4 3
4
5
6
CHAPTER
2
Nucleophilic Attack at Carbon Nucleophilic Attack at Halogen Nucleophilic Attack at Other Atoms Miscellaneous Reactions of Phosphines
1 4
7 9 9
12 12 12 13 15
Halogenophosphines
17
3.1 Preparation 3.2 Reactions of Halogenophines
17 17
Phosphonium Salts
19
4.1 Preparation 4.2 Reactions of Phosphonium Salts
19 22
p,-Bonded
23
Phosphorus Compounds
Phosphirenes, Phospholes and Phosphinines
31
References
36
Pentaco-ordinated and Hexaco-ordinated
Compounds By C.D. Hall
1
Introduction
48
2
Structure, Bonding and Ligand Reorganization
48
vii
...
Contents
Vlll
3
Acyclic Phosphoranes
49
4
Ring Containing Phosphoranes
52
4.1 Monocyclic Phosphoranes
52 55
Hexaco-ordinated Phosphorus Compounds
58
References
64
4.2
5
CHAPTER
CHAPTER
3
Bicyclic and Tricyclic Phosphoranes
Phosphine Oxide and Related Compounds
By B .J. Walker
Preparation of Phosphine Oxides
66
Structure and Physical Aspects
68
Reactions at Phosphorus
68
4
Reactions at the Side-Chain
68
5
Phosphine Oxide Complexes
71
References
75
4
Tervalent Phosphorus Acids By 0. Dahl
1
Introduction
77
2
Nucleophilic Reactions
77
2.1 Attack on Saturated Carbon 2.2 Attack on Unsaturated Carbon 2.3 Attack on Nitrogen, Chalcogen, or Halogen
77 79 79
Electrophilic Reactions
82
3.1 Preparation 3.2 Mechanistic Studies 3.3 Use for Nucleotide, Sugar Phosphate,
a2
3
3.4 Miscellaneous
a7 91
4
Reactions involving Two-co-ordinate Phosphorus
93
5
Miscellaneous Reactions
93
References
97
Phospholipid or Phosphoprotein Synthesis
CHAPTER
a4
5
Quinquevalent Phosphorus Acids By R.S. Edmundson
1
Phosphoric Acids and their Derivatives 1.1 Synthesis of Phosphoric Acids and their
102
Derivatives
102
Derivatives
119
1.2 Reactions of Phosphoric Acids and their
ix
Contents 1.3 Uses of Phosphoric Acids and their
Derivatives
2
Phosphonic and Phosphinic Acids and their Derivatives
2.1 Synthesis of Phosphonic and Phosphinic
CHAPTER
132
Acids and their Derivatives
132
and Phosphinic Acids and their Derivatives
169
2.2 Reactions and Properties of Phosphonic 3
132
Structures of Quinquevalent Phosphorus Acid Derivatives
18 3
References
184
6
Nucleotides and Nucleic Acids By R. C o s s t i c k
I
Introduction
196
2
Mononucleotides
196
2.1 Nucleoside Acyclic Phosphates 2.2 Nucleoside Cyclic Phosphates
196 206
3
Nucleoside Polyphosphates
206
4
Oligo- and Poly-nucleotides
2 13
4.1 DNA Synthesis
2 13
4.1.1 Chemical Synthesis 4.1.2 Enzymatic Synthesis 4.2 RNA Synthesis
2 13 2 16 2 17
4.2.1 Chemical Synthesis 4.2.2 Enzymatic Synthesis
2 17 220
4.3 Modified Oligonucleotides
220
4.3.1 Oligonucleotides Containing Modified
Phosphodiester Linkages
220
Sugars Oligonucleotides Containing Modified Bases
229
4.3.2 Oligonucleotides Containing Modified 4.3.3
232
Oligonucleotide Labelling, Conjugation and Affinity Studies
241
Nucleic Acid Triple-Helices and Other Unusual Structures
247
Cleavage of Nucleic Acids Including SelfCleaving RNA
250
Interaction of Nucleic Acids with Small Molecules
255
Contents
X
9 10
CHAPTER
7
Interaction of Metals with Nucleic Acids
262
Analytical and Physical Studies
265
References
268
Ylides and Related Compounds
By B.J.
Walker
I
Introduction
277
2
Methylenephosphoranes
277
2.1 Preparation and Structure 2.2 Reactions of Methylenephosphoranes
277 279
2.2.1 Aldehydes 2.2.2 Ketones 2.2.3 Ylides Co-ordinated to Metals 2.2.4 Miscellaneous Reactions
CHAPTER
279 283 283 283
3
The Structure and Reactions of Phosphonate Anions
289
4
Selected Applications in Synthesis
295
4.1 4.2 4.3 4.4
Carbohydrates Carotenoids, Retenoids and Pheromones P-Lactams Leukotrienes, Prostaglandins and Related Compounds 4.5 Macrolides and Related Compounds 4.6 Nitrogen Heterocycles 4.7 Miscellaneous Reactions
295 295 295
References
306
Introduction
313
Acyclic Phosphazenes
313
Cyclophosphazenes
323
Cyclophospha (thia)zenes
334
Miscellaneous Phosphazene Containing Ring Systems Including Metallophosphazenes
334
6
Poly(phosphazenes)
336
7
Molecular Structure of Phosphazenes
344
References
348
8
AUTHOR INDEX
297 297 301 301
Phosphazenes B y C.W. Allen
360
1
Phosphines and Phosphonium Salts BY D. W. ALLEN
1
Introduction
The past year has seen the appearance of the first volume of a major new work in the Saul Patai series on "The Chemistry of Functional Groups", concerned with the chemistry of organophosphorus compounds. This volume contains much of interest to readers of this chapter, reviewing the chemistry of primary, secondary, and tertiary phosphines, polyphosphines, and heterocyclic organophosphorus(II1) compounds. The Proceedings of the International Conference on Phosphorus Chemistry, held in Tallinn, USSR, in July 1989, have now been published, a significant amount of the work reported being relevant to the sections below, but which has not been reviewed further herein.2 Also of note are a number of reviews covering the generation and use of diorganophosphide reagents in the synthesis of phosphines , new methods of preparation of optically active phosphines for enantioselective transition metal catalyst systems, the application of the diphosphine BINAP(1) as a chiral element in asymmetric catalysis, and the chemistry of stable Mathey has reviewed three areas in which his phosphinocarbenes the chemistry of group has made significant contributions &y phospholes and related rr-complexes , the chemistry of 3-membered carbon-phosphorus heterocycles, and the reactions of coordinated phospha-alkenes.
.
2
PhosDhines
2.1 PreDaration 2.1.1 From HaloaenophosDhines and Oraanometallic Reaaents.A Grignard procedure has been described which enables the synthesis of large quantities (g1 mole) of trimethylphosphine from the reaction of methylmagnesium bromide with triphenylphosphite.l o High yields of tertiary alkylphosphines have been obtained from the reactions of Grignard reagents with the phosphorochloridite (2).l1 1
2
Organophosphorus Chemistry
Q
PPh,
~
p
p
n PR2
R2P (5)
h
Me
z
(3)
BuP ‘ , /c C ‘C iC HH
R = Menthyl
& c
PPh2
gPCH2CH2P@
(6)
A
/
&PPh2
0-
(9) R = Me, Et, Pr’, But, or Ph
v
(10)
4-1;. “-6””’ -1
NHMe
(14)
PPh2
R = H or PPh2
Me (17)n = 1 o r 2
n
1: Phosphines and Phosphonium Salts
3
Grignard procedures have also been employed in the synthesis of a range of hindered triarylphosphines, e.g. , ( 3 ) ,l2 and the chelating diphosphines ( 4 ) l3 and (5). l4 The reaction of f-butyldichlorophosphine with ethynylmagnesium bromide has given the dialkynylphosphine (6) from which macroheterocyclic polyphosphine systems involving alkynyl units have been prepared.l 5 An alternative route to the chelating diphosphole ligand ( 7 ) is provided by the reaction of 2,2'-dilithiobiphenyl with 1,2-bis(dich1orophosphino)ethane. Lithiation of chlorophenyl precursors with lithium metal, followed by treatment with chlorodiphenylphosphine, has been used in the synthesis of the new chiral diphosphines ( 8 ) .l 7 The "phospha[ 3 3 radialene" system ( 9 ) is formed in the reactions of 3,4-dilithio-2,5-dimethyl-2,4-hexadiene with organodichlorophosphines.l8 Two reports have appeared of the reaction of 3-lithiated D-camphor with chlorodiphenylphosphine. Treatment of the lithium reagent with 0.5 mole of the halogenophosphine results in the formation of the phosphino-enolate (10) as the only product. However, when 1.0 mole of the halogenophosphine is used, the main product is the 3-exo-phosphine (11) together with some of the 3-endo-isomer (12).19 On standing in solution the latter becomes the main product, and, indeed, is the only product reported by a second group.20 The generation of organolithium reagents by the direct metallation of acidic carbon substrates continues to be widely employed in the synthesis of phosphines. Direct o-metallation of methoxybenzene by butyllithium in the presence of tetramethylethylenediamine has been used in an improved route to tris-(o-methoxypheny1)phosphine (13).21 The o-phosphino-N-alkylanilines (14) have been prepared by the reactions of chlorodiphenylphosphine with the products of ortholithiation of the lithium salts of N-methyl-N-phenyfcarbamates, followed by acid decomposition of the intermediate phosphinocarbamates.22 A range of phosphines, e.g. , (15), has been prepared by the reactions of halogenophosphines with the product of ortho-metallation of N,N,N',N'-tetramethyl-P-phenylphosphonothioic diamide.23 Metallation of ferrocene with an excess of butyl-lithium, followed by treatment with dichloro(phenyl)phosphine, has led to the isolation of the chiral (but unresolved) phosphine (16).24 Lithium reagents derived from tetramethylcyclopentadiene have been employed in the synthesis of the unsaturated phosphines (17), whose coordination chemistry has also attracted some attention.25 The new chiral phosphine ligand
Organophosphorus Chemistry
4
(18) has been synthesised in the coordination sphere of iron by the reaction of a lithium enolate precursor with chlorodiphenylphosphine.26 The synthesis of the first closo-phosphacarborane system has been reported, utilising the reaction between a diorganometallic derivative of a dicarborane, with 2,4,6-tris-tbutylphenyldichlorophosphine 27 Other monophosphino derivatives of dicarboranes have also been prepared.28
.
2.1.2 Preoaration of PhosDhines from Metallated Phosphine6.- The past year has seen a significant increase in the number of papers describing the generation of metallophosphide reagents, and their use in synthesis. A range of new diphenylphosphido-metal derivatives has been prepared by the electrochemical oxidation of metals in acetonitrile solutions of diphenylphosphine 29 Treatment of the secondary phosphine ( But2SiF)2PH with butyllithium yields the cyclic zwitterionic phosphide (19) which does not involve a lithium-phosphorus interaction.30 A procedure for the synthesis of tris(trimethylsily1)phosphine and its conversion to lithium bis( trimethylsily1)phosphide has been published.31 This, and related silylphosphide reagents, have found extensive use in the synthesis of new polyphosphorus systems.32-39 Simple binary inorganic phosphide reagents have also continued to find application for the synthesis of novel cyclopolyphosphines, the contributions of Fritz et a1,40-43 and Baudler g& .144-51 being especially notable. Interest is growing in the synthesis and structural characterisation of phosphido-derivatives of aluminium,52 gallium,53-57 and indium,5 8 , 5 9 since thermal decomposition of such compounds may offer novel routes for the preparation of metallophosphide electronic devices. Metallophosphide reagents have also found use in the synthesis of cyclic stannylphosphine systems, e.g. , ( 2 0 ) .60t61 Applications of phosphinomethanide anions in synthesis continue to appear.6 2 Substitution reactions of neopentyl and cyclohexyl halides with the diphenylphosphide ion in liquid ammonia appear to proceed via the SRNl m e ~ h a n i s m . ~ The ~ , ~reactions ~ of ally1 halides with lithium diphenylphosphide have given the allylphosphines ( 2 1 ) 65 As expected, phosphide reagents attack the carbon atom of imines derived from aromatic amines, and, after protonation, N- (phosphinomethy1)arylamines (22) can be isolated.66 The reactions with epoxides of dilithium mono-organophosphides derived from primary phosphines proceed as would be predicted with ringopening to form the bis (hydroxyethy1)phosphines (23) 67
.
.
.
5
1: Phosphines and Phosphoniurn Salts
Ar NHC H2P(
Ph,PCH2CH=CR1 R2 (21) R'R2 = H or Me
R'COP
Cl CI -"1 CI I R
63
'
R (101a, b)
(1OOa, b)a; R = cyclo-C6H11
b; R = P r '
(1 02a, b)
(103a, b)
'
a E S i M e 3
PX5
L
(104a-d) a; E = NMe b; E = O
(105a-c) a; X = F
E=S d; E = N - p y C;
(py = 2-pyridyl
b; X =CI
C;
X=CF3
(106a-h) a; X = CI; E = NMe b; X = F ; E = N M e C ; 3X = CI; X = CF3; E = NMe d; X = C I ; E = G e; X = F ; E = O f; X = F ; E = S 9; X = CI; E = N-py h ; X = F; E = N-py
07a, b)a; R = b; R =
c > N -COCH3 I
R (108a, b) a; R = CI b; R = O E t
7
64
Organophosphorus Chemistry
pyridine ligands (104a-d) with 5-halogenophosphoranes (105a-c) also yields a series of neutral hexaco-ordinate phosphorus compounds (106a-h)by elimination of trimethylsilyl halide. The structures were evidenced by the high field of 31P n.m.r. (6,-135 to -202)and by the single crystal X-ray structure of (106a). Saturation transfer n.m.r. experiments indicate that the fluorine exchange in (106b) involves two competitive processes of the opened ring intermediate, both of which had similar energy barriers of 57.8kJ mo1-l for pseudorotation and 56.1kJ mol-l for ligand rotation. Both two co-ordinated phosphorus compounds (107ab) and trico-ordinated phosphorus compounds (108ab) have been shown t o react with catechol (109) in the presence of triethylamine to form the hexacoordinate structure (110).34 In conclusion, therefore, one can see that, although interesting chemistry is still emerging from the field of hypervalent phosphorus , the excitement generated in the early stages of the study of these compounds is beginning to subside. One of the most gratifying features of the work to date, however, has been the application of principles established in the phosphorus arena to the chemistry of elements other than phosphorus in and beyond the third row of the Periodic Table.
REFERENCES 1. K.C.K.Swamy, S.D.Burton, J.M.Holmes, R.O.Day and R.R.Holmes, Phosphorus, Sulfur and Silicon, 1990,53,437. 2. E.Magnusson, J.Am.Chem.Soc., 1990, 112, 7940. 3. C.J.Cramer, J.Arn.Chern.Soc., 1990,112, 7965. 4. P.Wang, Y.Zhang, R.Glaser, A.E.Reed, P.von R. Schleyer, and AStreitwieser, J.Am.Chem.Soc., 1991,113, 55. 5. S.D.Barton, K.C.K.Swamy, J.M.Holmes, R.O.Day a n d R.R.Holmes, J.Am.Chern.Soc., 1990,112, 6104. 6 . K.C.K.Swamy, R.O.Day, J.M.Holmes and R.R.Holmes, J.Am.Chem.Soc., 1990,112, 6095. 7 . K.B.Dillon and T.A.Straw, J.C.S.Chem.Commun., 1991, 234. 8 . V.F.Mironov, E.N.Ofitserov, I.V.Konovalova, P.P.Chernov, and A.N.Pudovik, Bull.Acad.Sci. USSR, (EngLtransl.) 1991, 40, 1929. 9. T. Kaukorat, P.G.Jones and R. Schmutzler, Chem.Ber., 1991,124,1335. 10. R.L.Wells, A.P.Purdy and C.G.Pitt, Phosphorus, Sulfur and Silicon, 1991,, 67,l. 11. R.M.Moriarty, J. Hiratake and KLiu, J.Am.Chem.Soc., 1990,112, 8575. 12. V.V. Ovchinnikov, Yu.G. Safina and R.A. Cherkasov, J.Gen.Chern. USSR, (Engl. transl) 1990,60,878. 13. I.V.Konovalova, L.A. Burnaeva, V.F. Mironov, I.V.Loginova, a n d A.N.Pudovik, Bull Acad.Sci. USSR,(Englhansl.) 1991, 40, 2612. 14a. V.F.Mironov, T.N.Sinyashina, E.M.Ofitserov, E.I.Gol'dfarb, I.V.Konovalova, a n d A.N.Pudovik, J.Gen.Chem.USSR (EngLtransl) 1990, 60, 846. 14b. E.N.Ofitserov,V.F.Mironov,T.N.Sinyashina,T.V.Konovalova, J.Gen.Chem. USSR (Engl. transl), 1990, 60, 33. 15. V.F. Mironov, E.I.Gol'dfarb, P.P.Chernov, I.V. Konovalova, and A.N.Pudovik, Bull. Acad Sci. USSR (Engl.transl), 1990, 39,1319. 16. C.K.McClure and K.-Y.Jung, J.Org.Chem., 1991,66, 867.
2:
Penraco-ordinated and Hexaco-ordinated Compounds
65
17. C.K.McClure and K-Y. Jung, J.Org.Chem., 1991,66, 2326. 18. S.S.Kumarave1, S.S.Krishnamurthy, R.O.Day and R.R.Holmes, Phosphorus, Sulfur and Silicon, 1991,67, 163. 19. P.G.Jones and R. Schmutzler,Phosphorus, Sulfur a n d Silicon, 1991,66,173. 20. K.C.K.Swamy, J.M.Holmes, R.O.Day and R.R.Holmes, J.Am.Chem.Soc., 1990,112,6092. 21. J.H.Yu, A.M.Arif, and W.G. BentrudeJ.Am.Chem.Soc., 1990,ll2,7451. 22. A.A.Prishchenko, M.V.Livantsov, P.V.Zhut-skii, D.A.Pisamitskii, N.M.Shagi-Mukhametova and V.S.Petrosyan,J.Gen.Chem.,USSR (EngLtransl) 1990, 60, 398. 23. A.Murillo, L.M.Chiquete, P.Joseph-Nathan and R.Contreras, Phosphorus, Sulfur and Silicon, 1990,53,87. 24. S.A. Terent'eva, N.A.Pudovik, and A.N.Pudovik, J.Gen. Chem.USSR, 1990, 60, 397. 25. Y. Vannoorenberghe and G.Buono, J.Am.Chem.Soc., 1990,112, 6142. 26. L.I.Mizakh, L.Yu Polonskaya, A.N.Gvozdetskii, and L.B.Karpunina, J.Gen.Chem. USSR,1990,60,1274. 27. A.Filali, J.-J.Yaouanc, and H. Handel, Angew. Chem.Znt.Ed.Engl., 1991, 30, 560. 28. B.N.Anand, R.Bains and Km. Usha, J.Chem.Soc., Dalton Trans., 1990, 2315. 29. D.C.Apperley and R.K.Hams, Phosphorus, Sulfur and Silicon,1990,54,227 30. E.K.Rutkovskii, I.S.Zal'tsman, N.G.Feshchenko and A.M.Pinchkuk, J.G'en.Chem. USSR,1990,60,1491. 31. I.S.Zal'tsman, G.K.Bespal'ko, A.P.Marchenko, A.M.Pinchuk, A.D.Sinitsa, a n d S.K.Tupchienko, J.Gen.Chem. USSR,1990,60, 1942. 32. DKKennepohl, B.D.Santarsiero,and R.G.CavellJnorg.Chem., 1990,29,5081. 33. D.K. Kennepohl, A.A.Pinkerton, Y.F.Lee and R.G. Cavell, Znorg.Chem., 1990, 29, 5088. 34. R.Chen and B.Cai, Phosphorus, Sulfur and Silicon, 1991,67,83.
3
Phosphine Oxides and Related Compounds BY B. J. WALKER
1 Preparation of Phosphine Oxides Nickel bromide is reported to catalyse the arylation of amorphous red phosphorus with iodobenzene to give a temperature dependent mixture of triphenylphosphine oxide and tetraphenylphosphonium iodide.] Since the latter compound can be hydrolysed to the former the method provides a synthesis of triphenylphosphine oxide in almost quantitative yield. Monoand tri-3-sulphonate-substituted triphenylphosphines' react with activated alkynes in water to give new hydrophilic phosphine oxides (1) or vinylphosphonium salts or alkenes depending on the pH and the nature of the acetylene.2 Chiral di- and tri-arylphosphine oxides have been prepared in 9 5 % enantiomeric excess by sequential nucleophilic displacement reactions on the phosphorus oxide (2) derived from ( l R , 2S)-ephedrine.3 Xray analysis was used to determine the absolute configuration at phosphorus for both (2) and a further reaction intermediate. The phosphine oxide (3)4 and difluoromethyldiphenylphosphine oxide (4)5 have been prepared, the l a t t e r by the reaction of chlorodifluoromethane with diphenylphosphine oxide, for use in the synthesis of fatty acids and difluoroalkenes, respectively. However reactions of (3), and the corresponding phosphonium salt, with carbonyl compounds gave only poor yields of alkenes. Olefination reactions with ( 4 ) gave moderate yields of difluoroalkenes but attempts at extension to the synthesis of monofluoroalkenes by the use of monofluoromethyldiphenylphosphine oxide were unsuccessful.^ The yneeneallenylphosphine oxides ( 6 ) have been synthesized, as potential DNA cleaving and anti-tumour agents, from the alcohols ( 5 ) . 6 In solution compounds (6) readily cyclise to aromatic structures (7). A variety of phosphine oxides (9) have been prepared from vinylphosphonium salts (8) for use in the synthesis of chiral phosphinocarboxylic acid ligands.7 The cycloaddition of alkynyldiphenylphosphine oxides to 1,3h3-azaphosphinines (10) provides a route to 2-diphenylphosphinoxido-h~-phosphinines(11) - 8 Phosphine radical cations, generated by one-electron oxidation of phosphines with excited singlet 1,4-dicyanonaphthalene, form phosphine oxides on reaction with water.9 Alkyldiphenylphosphine oxides (12) and sulphides (13) have been conveniently prepared in moderate yield by the 66
3: Phosphine Oxides and Related Compounds
67
0
0
II
II
Ar2-" PhPCH=CHR
4s03Na
n-cll
(1) A r =
(2)
F2CHPPh2 H23
(3)
(4)
n = 1,2
(8) n = 2, 3
(9) x =
'-' U'
CHO, C02Me, C02H
n =2,3
Ph
0
II
RCECPPh2 Ph
X
II
PhZPCI
Sm12
+
RX'
'
r. t.
*
X
II
Ph2PR (12) x = o (13) X = S
68
Organophosphorus Chemistry
reaction of chlorodiphenylphosphine oxide or sulphide, respectively, with alkyl halides in the presence of samarium diiodide.10 Macrocyclic phosphine oxides ( 1 6 ) have been synthesized by the reaction of halogenated diphosphine dioxides (14) with the diphosphine (15) followed by alkaline hydrolysis of the phosphonium salt formed.11
2 Structure and Physical Aspects The structural parameters of the 1:l crystalline adducts (17) formed from diphenylphosphine oxide and azodicarboxylates have been determined by X-ray analysis.12 X-ray methods have also been used to show that the structure of the product from the reaction of 1H-phosphole l-oxide (18) with dichlorocarbene is (19 ) , a 1,4-dihydrophosphinine rather than the phosphepine structure previously reported.13 The X-ray crystal structure of tris(chloromethy1)phosphine oxide has been reported. 1 4 Substitution effects on 31P and 13C n.m.r. spectra of a number of tris(4substitutedpheny1)phosphine oxides have been investigated. 15 A variety of studies, including ones of surface modification and thermal stability, on poly(ary1ene ether phosphine oxides) have been reported.16 3 Reactions at Phosphorus Phosphine-boranes (20) have been synthesized directly from phosphine oxides without isolation of the intermediate phosphine.17 The thermal elimination of water from phosphorus-oxygen compounds, including phosphine oxides, in the gas phase has been investigated.18 4 Reactions at the Side-Chain Phosphine oxide-based olefin synthesis continues to be used although rather less than might be expected in view of the opportunities for controlling stereochemistry that the method offers. Both (Z)-penta-2,4-dien-l-01 ( 2 2 ) and substituted (E)-penta-2,4-dien-l-ols (24) have been synthesized by this method.19 Synthesis of the (2)-isomer (22) involves the use of the furan Diels-Alder adduct (21) to establish the (Z)-stereochemistry (Scheme 1). The (E)-isomers (24) are available by a more general route via (23). The Diels/Alder-active (E,E)- 1-methoxy-4-trimethylsilyl-l,3-butadiene (26) has been prepared by the reaction of methoxymethyldiphenylphosphine oxide anion with trans-trimethylsilylpropenal followed by separation and decomposition of the (RS.SR)-2-hydroxyalkylphosphine oxide adduct (25).20 Sequential reaction of the carbanions of a-methoxyallyl(dipheny1)phosphine oxides with alkyl chloroformates and aldehydes provides a general, convenient, one-pot route to 4-methoxyalka-2,4-dienoates (27) (Scheme 2).2 1 High diastereofacial selectivity is observed in the intermolecular
3: Phosphine Oxides and Related Compounds
69
Ph2P(CH2)3PPh2
(16) n =2,3
Me
Me
M
PO h '/
PTC NaOH, HzO, CHC13
-
-d-.; o"
\ Ph
70
Organophosphorus Chemistry
@FPh2
i
H
w
ii
i
P
h
2
*
H
OH iii, iv
/
OH
H
OCOAr
R2
01
R3
? I +
vi, vii
Ph2P R2
0
R3 OH
+
OH
R4
(23)
(24)
II
Reagents: i, Ph2PCH2Li;ii, NaBH4;iii, NaH; iv, ArCOCI, DMAP, CH2CI2;v, 170 "C, 8 mins; vi, 2 x BuLi; vii, R42C0
Scheme 1 OMe
Reagents: i, 2.2 x LDA; ii, CIC02R3;iii, R4CH0
Scheme 2
3: Phosphine Oxides and Related Compounds
71
pinacol cross-coupling of a,a-disu bsti tuted a - ( d i p h e n y l p h o s p h i n o y 1 ) acetaldehydes to give ( 2 8 ) . 2 2 On treatment with base the diols (28) provide a stereospecific synthesis of 3,3-disubstituted allylic alcohols (Scheme 3). Phosphine oxide-based olefinations of allenyldiphenylphosphine oxides ( 2 9 ) have been used to provide a short synthesis of [3]-cumulenes ( 3 0 ) (Scheme 4)?3 Olefination reactions with the phosphine oxide (31, X=H) have been used to synthesize a variety of vitamin D analogues including the first example ( 3 2 ) of a (7Z)-isomerz4 and the key step in a short, flexible synthesis of 25-functionalised vitamin D3 analogues (33).*5 The individual enantiomers of (E)-but-2-enyl-t-butylphenylphosphine oxide ( 3 6 ) have been prepared from the corresponding (+)-( 3 4 ) - and (-)-(3 5 ) - t b u t y l m e t h y l p h e n y l p h o s p h i n e oxides.26 Under basic conditions each of the enantiomers of (36) react 100% stereoselectively with 2-methylcyclopent2-enone to generate enolates (37), which in turn react with 4-chlorobut-3en-2-one to give ( 3 8 ) . Compound ( 3 8 ) can be converted into the hydrindenone ( 3 9 ) which is suitable for conversion into vitamin D analogues. Both phosphine o x i d e - ( 4 2 ) and phosphonate-(43) c a r b a n i o n s , prepared from the corresponding allenes ( 4 0 ) and ( 4 1), undergo carbanion-accelerated Claisen rearrangement at room temperature with complete regioselectivity to give ( 4 4 ) .27 Kinetic and stereochemical studies of the intramolecular Diels-Alder reactions of cycloalkenylallenylphosphine oxides ( 4 5 ) have been reported.28 G ern -dialkyl effect accelerations and differences in rate due to the allene-ene tether length were observed and measured. The thermal 1,3-dipolar cycloaddition of N-benzylidene-a (dipheny1phosphinoyl)glycine esters (46) to N-phenyl maleimide has been investigated.29 The reaction involves rate-determining dipole formation and gives good yields of two diastereomeric endo adducts ( 4 7 ) and ( 4 8 ) . With less reactive dipolarophiles the dipolar cycloaddition reaction is the ratedetermining step.30 The reaction has been used to provide a route to polyfunctionalised 2-(diphenylphosphinoy1)pyrrolidines with generally good P-syn 4-endo selectivity. A study of the cycloaddition of nitrones to vinylphosphine oxides, sulphides and selenides to give (49) and (SO) shows that the regio- and diastereo-selectivity of the reactions varied widely depending on the substituents and the conditions used.3 1 Both diazo derivatives ( 5 1) and nitrilimines (52) have been synthesized by the reaction of the lithium salts of phosphorus-substituted diazomethanes with chlorophosphi nes .3 2 5 Phosphine O x i d e Complexes The bimetallic, bis(phosphine oxide) complex (53) has been prepared by the
Organophosphorus Chemistry
72
Reagents: i, [V2C13(THF)6]2[Zn2CIe]; ii, excess NaH
R2F OH
Scheme 3 0 I1
Rbc+pph2
i, ii
H
R2
5
(29) Reagents: i, KN(SiMe3)2,THF, -78 “C; ii, R2R3C0
Scheme 4
Ph,P=O I
+
X = Li ___)
R’O’.’ 0
R2 =
TBSO-.’
.‘-Y
HO’
Me OH
(32) R’ = R2 = H
73
3: Phosphine Oxides and Related Compounds 0
0 II
(34)
(35) 0-
c"('".."'t 0 II
Ph
0
(39)
? (40)2 = Ph2P(O-)
,
R4
R4 R3
(42)Z = Ph,P(O) (43)2 = (Bu'O),P(O)
(41) Z = (Bu'O),P(O)
(44)
74
Organophosphorus Chemistry
Ph
3:
Phosphine Oxides and Related Compounds
75
reaction of the corresponding biphosphine with Co(I1) chloride followed by treatment
with
hydrogen
peroxide.33
determined by X-ray crystallography.
T h e structure of ( 5 3 )
has been
Reports of examples of the synthesis
of phosphine oxides incorporated in metallocyclic rings include the platinum complex (54);34 the structure (54) has been confirmed by X-ray diffraction studies.
Structural
studies
of
phosphine
oxide-uranium
complexes,35~36
including an X-ray structure of tetrabromobis-[tris(pyrrolidinyl)phosphine oxide] uranium(IV),36 have been reported. REFERENCES 1.
H-J. Cnstau, J. Pascal, and F. Plenat, Tetrahedron Letters, 1990, 31,
2.
C. Larpent, G. Meignan, and H. Patin, Tetrahedron, 1990, 46, 6381.
3.
J.M. Brown, J.V. Carey, and M.J.H. Russell, Tetrahedron, 1990, 46, 4877.
4.
A. Stoller, C. Mioskowski, C. Sepulchre, and F. Bellamy, Tetrahedron Letters, 199 1 ,
5463.
32, 495. 5.
M.L. Edwards, D.M. Stemerick, E.T. Jarvi, D.P. Matthews, and J.R. McCarthy,
6.
K.C. Nicolaou, P. Maligres, J. Shin, E. de Leon, and D. Rideout, J. Am. Chem. SOC., 1990, 112, 7825.
7.
Y. Okada, T. Minami, Y. Sasaki, Y. Umezu, and M. Yamaguchi, Tetrahedron Letters,
8.
G. Markl, F.G. Klarner, and C. Lodwig, Tetrahedron Letters, 1990, 31, 4589.
Tetrahedron Letters, 1990, 31, 5571.
1990, 31, 3905. 9.
G. Pandey, D. Pooranchand, and U.T. Bhalerao, Tetrahedron, 1991, 47. 1745.
10.
M. Sasaki, J. Collin, and H.B. Kagan, Tetrahedron Letters, 1991, 32, 2493.
11.
M. Vincens, J.T. Grimaldo-Moron, and M. Vidal, Tetrahedron, 1991, 37, 403.
12.
D. Camp, P.C. Healy, I.D. Jenkins, B.W. Skelton, and A.H. White, J . Chem. SOC., Perkin Trans.1, 1991, 1323.
13.
G. Keglevich, A. Szollosy, L. Toke, V. Fulop, and A. Kalman, J. Org. Chem., 1990, 55,
6361. 14.
A.N. Chekhlov, Y.G. Kulishov, S.E. Tkachenko, and E.N. Tsvetkov, Bull. Acad. SC.
USSR, 1990, 39, 1406.
15. 16.
W-N. Chou and M. Pornerantz, J. Org. Chem., 1991, 56, 2762. H.F. Webster, C.D. Smith, J.E. McGrath, and J.P. Wightman, Abstracrs of American Chemical Society, 1991, 202, Aug. p.52; ibid, p. 53; ibid, p. 54.
17.
T. Irnamoto, T. Oshiki, T. Onozawa, T. Kusumoto, and K. Soto, J . Am. Chem. SOC.,
18.
H. Bock and M. Bankmann, Z. Anorg. Allg. Chem., 1991, 606, 17.
19.
P.S. Brown, N. Greeves, A.B. McElroy, and S. Warren, J. Chem. SOC., Perkin
20.
J.T. Pegram and C.B. Anderson, Tetrahedron Letters, 1991, 32, 2197.
21.
E.F. Birse, M.D. Ironside, L. McQuire. and A.W. Murray, J. Chem. S O C . , Perkin
1990, 112, 5244.
Trans.1, 1991, 1485.
Trans.], 1990, 2811.
Organophosphorus Chemistry
76 22.
J. Park and S.F. Pederson, J. Org. Chem., 1990, 55, 5924.
23.
I. Saito, K. Yamaguchi, R. Nagata, and E. Murahashi, Tetrahedron Letters, 1990, 31, 7469. M.M. Maestro, F.J. Sardina, L. Castedo, and A. Mourino, J. Org. Chem., 1991, 5 6 .
24.
3582. 25.
J.L. Mascerenas, J. Perez-Sestelo, L. Castedo. and A. Mourino, Tetrahedron Letters,
26.
1991. 32, 2813. R.K. Haynes, J.P. Stokes, and T.W. Hambley, J. Chem. Soc., Chem. Commun., 1991, 58.
27. 28. 29. 30.
S.E. Denmark and J.E. Marlin, J. Org. Chem., 1991, 56, 1003.
M.L. Curtin and W.H. Okamura, J. Org. Chem., 1990, 55, 5278.
J.J.G.S. van Es, K. Jaarsveld, and A. van der Gen, J . Org. Chem., 1990, 55, 4063.
J.J.G.S. van Es, A. ten Wolde, and A. van der Gen, J. Org. Chem., 1990, 55, 4069.
31.
A. Brandi, S. Cicchi, A. Goti, K.M. Pietrusiewicz, and W. Wisniewski, T e t r a h e d r o n ,
32.
M. Granier, A. Baceiredo, Y. Dartiguenave. M. Dartiguenave, H-J. Menu, and G.
33.
S.I. Al-Resayes. P.B. Hitchcock, and J.F. Nixon. J. Chem. SOC., Chem. Commun.,
34.
R.D.W. Kemmitt, S. Mason, M.R. Moore, J. Fawcett, and D.R. Russell, J. Chem. Soc.,
35.
Chem. Commun., 1990, 1535. G.S. Conary, R.L. Meline, L.J. Candle, E.N. Duesler, and R.T. Paine, Inorg. Chem.
1990. 46, 7093.
Bertrand, J. Am. Chem. SOC.,1990. 112. 6277.
1991, 78.
Acta, 1991, 189, 59.
36.
J. G. H. Dupreez, H. E. Rohwer, B. J. A. M. Vanbrecht, B. Zeelie, U. Castellato, and R. Graziani, Inorg. Chem. Acta, 1991, 189, 67.
4
Tervalent Phosphorus Acids
BY 0.DAHL
1 Introduction
The title of this chapter has been changed from Tervalent Phosphorus Acids because tervalent phosphorus acids don't exist! Derivatives of tervalent phosphorus acids, however, are abundant, and it is these, e.g. (RO)3P, RP(NR'2)2, and similar compounds with at least one P-N, P-0, or P-Sbond, the chapter is about. A comprehensive review has appeared on the synthesis, structure, bonding, and reactivity of acyclic iminophosphines, R-P=N-R'.' Proceedings of the 9th International Round Table on Nucleosides, Nucleotides, and their Biological Applications, Uppsala, 1990, which contain many papers of relevance for this chapter, have been published.2
2 Nucleophilic Reactions 2.1 Attack on Saturated Carbon.- A modified Arbuzov procedure to prepare galactose-6-phosphatehas been p ~ b l i s h e dIt. ~involves an Arbuzov reaction of diphenyl isopropyl phosphite (1) with a protected 6-iodogalactoside(2); the merits of the phosphite (1) is that the isopropyl iodide formed does not compete with (2),and that the diphenyl phosphonate product can be easily converted to a dibenzyl phosphonate by base catalysed ester exchange and the latter reduced cleanly to the free phosphonic acid. Alkylation of the 1,3,2-oxazaphospholan (3) is the first step in a stereoselective synthesis of phosphinates and tertiary phosphine oxides. The phosphonium intermediates (4) are relatively stable when RX is reactive (methyl iodide, benzyl chloride) and have now been observed by n.m.r. to decompose to the Arbuzov products (5) with full r e t e n t i ~ n .Less ~ than full retention in the overall reaction is due to formation of both (4a) and (4b) from pure (3), probably because (4a) isomerises to (4b) via a phosphorane mechanism.
77
Organophosphorus Chemistry
78
R' = alkyl, aryl R2 = COOMe, CN
0' Ph2PCI
-
R2
-?% - 78 "C
PPh,
4:
Tervulent Phosphorus Acids
79
2.2 Attack on Unsaturated Carbon.- The well-known 2,3-sigmatropic rearrangement of ally1 phosphites to allylphosphonates has been used to obtain a series of substituted allylphosphonates ( 6 ) for use in Horner-Emmons reaction^.^ Surprisingly the products were pure Z-isomers for R 2 = COOMe but mainly Eisomers for R2 = CN. A similar rearrangement served to prepare some allenic phosphine oxides, e.g. (7),designed as DNA-cleaving molecules.6A full paper has appeared on the reactions of benzothiete (8) with trialkyl phosphites or dialkyl phenylphosphonites, e.g. (9);7the mechanism proposed is nucleophilic attack on the exocyclic carbon of ( 8 ) followed by an Arbuzov-type dealkylation. Tris(dimethy1amino)phosphine reacts at room temperature with arylaldehydes bearing electron-donating groups, or benzaldehyde, to give a-aminophosphonic diamides (10) which are useful for Horner-Emmons-type condensations.8 The addition reactions of in situ generated trimethylsilyl phosphites, phosphonites, or phosphinites (1 1) with imines, e.g. (12), have been ~ t u d i e dThe . ~ reactions are much faster than similar additions to aldehydes, and most substituents X are tolerated, although surprisingly the rate is decreased by electron-withdrawing groups; other C=N compounds like isocyanates and diarylcarbodiimides react similarly, but no reaction occurred with dicyclohexylcarbodiimide, hydrazones, or oxime ethers. Phosphites, and other tervalent phosphorus compounds, are effective reagents for the reduction of oxidatively damaged thymidine derivatives, e.g. (13);1° the reaction is thought to begin with attack at the carbonyl carbon as shown. Triethyl phosphite is unreactive towards phenyl isothiocyanate below 150 OC and removes sulphur to give phenyl isocyanide at higher temperatures; addition of acetic acid, however, results in the formation of a thiocarbamoylphosphonate (1 4) at room temperature.ll The same product is obtained from (15) and other tert.-butoxy compounds at room temperature without the addition of acid; obviously the addition product (16) must be trapped by protonation from an acid or a tert.-butyl carbocation in order for the reaction to proceed. Several thio analogues of phosphoenolpyruvate (17) have been prepared from ethyl bromopyruvate and the thio- or dithiophosphites
(18).12
2.3 Attack on Nitrogen, Chalcogen, or Halogen.- Azides react with phosphites to give phosphazides, e.g. (19), which normally undergo the Staudinger reaction to give phosphazenes,e.g. (20). In thecase of (20),a Wittig-type reaction with the carbonyl group then occurs to give (21).13The phosphazide intermediate (19, R = H),
Organophosphorus Chemistry
80
Ph
ArCHO
+
P(NMe2)3
d y\N l
R1R2P-OSiMe3 +
-
Me,? ArCH-P(NMe,), (1 0)
--x&
“NH P(O)R’R~
X (12)
(11)
R‘,R2 = OEt, OSiMe3, Ph
0 M e N y i e
0A N
A
OH
+(Ph0)3P
-
+
HO
P(OPh)3
MZ? ):
0
- (Ph0)3P =O ~
Me I
R
M e N p e OAN
A
OH
J- H*O
0
4:
Tervalent Phosphorus Acids
81
(18) R' = Me, Et, Pr' R2 = Pr', Bu, Ph n = 1,2
OCOMe Phk
'
-
(Pri2N)2P-P (NP$ 2 ) ~
(26)
X
N*P(OEt)3
(Pr'2N)2P-X-P(NPri2)2
(27)X
-
= S , Se, Te
Me Ph
?
(Et2Nc-S-12
(28)
82
Organophosphorus Chemistry
however, gave the triazole (22), probably via a 1,5-electrocyclisation to (23), instead of the usual Staudinger 1 ,4-cyclisation.14 Acylphosphonites (24) with one equivalent of hexafluoroacetone gave the phosphites (25), probably via attack of phosphorus on the oxygen of hexafluoroa ~ e t 0 n e . lThe ~ reactions of a-halogenated phenylnitromethanes with triethyl phosphite have been studied, and the different products rationalised by a mechanism which begin with attack of phosphorus on oxygen.16 Oxidation of tetrakis(diisopropy1amino)diphosphine(26) with elemental sulphur, selenium, or tellurium gave mostly the symmetrical diphosphinochalcogenides(27);” the crystal structures of (27, X = S , Te) were determined. Tetraethylthiuram disulphide (28) has been introduced as a reagent which can replace elemental sulphur for oxidation of oligonucleoside phosphites to phosphorothioates;18 the rate of oxidation is rather low (15 min on solid support), but the less hindered tetramethyl analogue gave mostly dealkylation of the phosphite instead of oxidation. The reactions of alkylbis(diisopropylamino)phosphines (29) with tetrachloromethane or bromotrichloromethane to give P-halogenoylides (30) which rearrange to halomethylphosphines (31) continue to attract interest. A kinetic study of the rearrangement of (30, X = CI, R = H)19 and further studies of the reactions of the bromo compounds20 have appeared.
3 Electrophilic Reactions 3.1 Preparation.- Several new chelating diphosphite ligands (32)21 and (33)22
have been prepared from phosphorus trichloride and the appropriate phenols or alcohols. The methylenebisphosphonites (34)23 and analogous bisphosphoramidites (35)23 and (36)24325 have also been made for studies of their chelating properties. Some thio- (37) and dithiophosphites (38) have been prepared from a thiol and the corresponding phosphorochloridite or -dichloridite.12 They are very sensitive towards oxidation and hydrolysis, and the thiophosphites (37) in particular rearrange easily to thiophosphonates (39); they could be used quickly, however, to prepare thio analogues of phosphoenol pyruvate (17). The first aminophosphines with two trichloromethyl substituents on phosphorus, (40), have been prepared as shown;26they are not easily hydrolysed and do not react with hydrogen chloride! Recent work on the reaction of phosphorus trichloride with aldehydes has resulted in the isolation of the primary products (41) and
4:
Tervalent Phosphorus Acids
83
R
(33) R = Ph, COOEt, COOP6
P(OR2)2 R~N’ \
(34) X = 0,s; Y = CH2 (35) X = 0,s;Y = MeN
RS-P (0Et)2
e
P(OR2)2
(36) R’ = Me, Ph R2 = CH2CF3,Pr’, Ph
E
R-P(OEt),
(RS),P-OMe
r.t.
(37) R = Pr’, But, 2-pyridyl
PC13 + RCHO
(39)
__
R3N
(38) R = Pr’, Bu
CI 1 RCH-O-PC12 (41) R = Pr, Pr‘
84
Organophosphorus Chemistry
the importance of acid and base catalysis has been realised; very pure phosphorus trichloride (distilled from N,N-diethylaniline) did not react at all with aldehydes! A series of polycyclic phosphites (42)were prepared from the corresponding tetrol and tris(dimethylamin~)phosphine.~~ There was no tendency of (42)to form the square-pyramidal H-phosphorane (43)but instead an internal dealkylation occurred to give the H-phosphonate (44). Exchange of amino groups in tris(dialky1amino)phosphineshas been used to prepare several new cyclic aminophosphines, e.g. (45)which is an efficient reagent for the determination of enantiomeric purity of alcohols,28 (46)which could not be obtained pure due to further condensation reactions,29 and (47)and (48).30 The 1,3,2-benzothIazaphospholen (49)was made from the phosphorodiamidite (50),31 and the 1,3,2-thiazaphospholan (51) from methyl phosphor~dichloridite,~~ in a search for new phosphorylating agents. Diethyl phosphorochloridite and N-acetonyiacetamide (52) gave the phosphite (53) which upon heating was converted to the isomeric phosphite (54) and subsequently to the 1,3,2-oxazaphospholen (55).33A similar initial attack on the amide group of (56) by ethyl phosphorodichloridite gave the 1,4,2-0xazaphospholen (57) which rearranged upon heating to (58).34The enimine (59) with phosphorus trichloride did not give the expected 1,2-azaphospholen (60),but the dihydro-l,2azaphosphorin (61).35
3.2 Mechanistic Studies.- Nucleophilic substitution reactions at tervalent
phosphorus centres are very often not stereoselective, but when the nucleophile is RLi the stereochemical result has usually been clean inversion. In a recent report, aimed at asymmetric synthesis of phosphines, the first substitution reaction on the borane adduct (62)gave mostly retention, while the next two steps both occurred with a high degree of i n ~ e r s i o nA. ~series ~ of tervalent phosphorus acid imidazolides, e.g. the phosphorimidazolide (63), has been prepared and the uncatalysed substitution of the imidazole group with methanol or diethylamine studied.37 In the case of (63),the primary product with methanol was the inverted phosphite, but with diethylamine the reaction was not stereoselective. Two salts of tris(dialky1amino)phosphines with tetrafluoroboric acid, (64)and (65),have been isolated.38According to 31P n.m.r. the proton is located on phosphorus, and the salts are extremely susceptible to alcoholysis.
4:
Tervalent Phosphorus Acids
x
A
\ (42) n
Me
+
(Me2N),P-OMe
NHMe
*
= 0-4
a s ) - o M e N Me
(50)
(49)
ASH
+MeOPCI2
0
NHMe
lB A>P-OMe Me
(51)
86
Organophosphorus Chemistry
J
0
EtOPC12
EtOJy
+
EtO' (56)
Et
)-+ 4 I
-1y-
+ PC13
Et
Pr
-D A
'?PAR 0-P,
0
OEt
(55) X, R = Me (58) X = OEt R = CF3, Ph
(57)
Bu
Bu
CI
N y R P-0
- EtOH
-
Pr
Bu I
Et
+
(Et2N)3P-H BF4-
(R0)2P-NEt2 (66) R = Me, Et, But, PhCH2, 4-BrC6H4CH2, Ph
(
X
o CH2C$)1-NPri2
(67)X = F, CI
PhCH20-P (NEt2)2
(68)
4:
Tervalent Phosphorus Acids
87
3.3 Use for Nucleotide, Sugar Phosphate, Phospholipid, or Phosphoprotein Synthesis.- A series of phosphoramidites (66) and (67) has been evaluated for use to prepare O-phosphorylserine and O-serine phosphorylated p e p t i d e ~ . ~The ~ - ~best l compromise between stability to the usual deblocking
reagents in the Boc peptide synthesis and ease of cleavage of the phosphorus protecting groups was found for (66, R = phenyl or 4-bromobentyl). The phosphoramidite (66, R = benzyl) has been used in an improved synthesis of dihydroxyacetone phosphate,42and the phosphoramidite (67, X = H) in the syntheses of some hexosamine-inositol phosphate^.^^ The phosphorodiamidite (68) was used to prepare a cyclic inositol phosphite which gave inositol phosphate diesters after oxidation and transesterification.44A guanosine 5'-diphosphate mannose analogue containing a hexadecyl phosphate group was obtained from the phosphorodiamidite (69).45 The 1,3,2-0xazaphospholan(70) undergo hydrolysis with opening of the ring under very mild conditions to give after oxidation the phospholipid (71).46Another approach to similar phospholipids involves the phosphoramidite (72), which is transformed to (73) under conditions that avoid base-catalysed acyl migrations and therefore give very pure products.47 Phosphoramidites containing reporter groups, e.g. biotin, are not new, but several improved reagents for labelling of oligonucleotides have been reported this year. These include the biotin reagents (74),48(75),49and (76),50all of which allow for multiple labelling with biotin, the protected biotin reagent (77)51which likewise allows multiple labelling, and (78)52which contains a dimethoxytrityl group on biotin for easy quantisation of the coupling efficiency. A reagent (79) containing a phosphotyrosine group makes possible the detection of oligonucleotides by antibodies specific for p h o s p h ~ t y r o s i n e .Some ~~ phosphoramidites (80) containing 2,2'bipyridyl groups were used to prepare nucleoside-bipyridine conjugates which cleaved RNA in the presence of copper(l1) ions.53 A previously reviewed method to prepare oligodeoxyribonucleotides or their phosphorothioate analogues has been further d e v e l ~ p e d . ~ The ~ , ~phosphite ~ monomers (81) are coupled to support-bound nucleoside using N-methylimidazole as catalyst and the products are hydrolysed to H-phosphonates (82) with water; capping with the phosphite (83) and hydrolysis after each coupling cycle was found necessary in order to obtain products of a reasonable purity. A full paper has appeared on the use of nucleoside alkyl phosphorochloridites (84), prepared in situ from the H-phosphonate diesters (85)and the dichlorophosphorane (86), for the
88
Organophosphorus Chemistry
J
Me3N
NPri, DMT -0-P' Biotin-NH-0 1 \O -cN +
(74)
(73) 0
(75)
MMTrO Biotin-NH
Biotin
4:
Tervalent Phosphorus Acids
89
(77)
(78)
NHFmoc (80) n = 4,11
(79)
DMTroY + - DMTro i, NMI
ii, H20
o@
PriO-P(OCH(CF3)2)2 (83)
Organophosphorus Chemistry
90
DMTrO
3” H ‘
RO’.
Br
(86)
(85) R = Me, CH2CH2CN
(84)
-rfzDMTro-vbz dT
(86)
DMTro
DM ,o,y
Br
0. Pri2N
’\ 50
0.
,P-CI Pri2N
H
OMTr0Y
R’ R ~ P -N ,
::
O ,
OSiButMe2
I PN -nO
O%CN (91) R1R2N= MezN, MeEtN,
n
Et2N, Pri2N, 0
uN
(92)
4:
Tervalent Phosphorus Acids
91
preparation of nucleotide dimers in solution and oligomers on solid support.56The yields were about 99% per step for the solid support synthesis of a Tle-mer which compare well with the phosphoramidite method. An in situ prepared phosphorochloridite (84, 6 = Tbz, R = Me) has further been used to obtain a H-phosphonothioate (87) which gave a phosphorodithioate (88) after oxidation with sulphur.57The reagent (86) could also be used to convert a H-phosphonamidate (89) to a dinucleoside phosphoramidite Preparation of RNA fragments by the phosphoramidite method has been . ~ ~the five uridine phosphoroptimised with regard to the amino s ~ b s t i t u e n t s Of amidites (91) tested, the ethylmethylamino compound was preferred. The dimethylamino compound decomposed by attempted column chromatography on silica, but the other phosphoramidites could be purified in this way. Of these (91, NR1R2 = NMeEt) gave the fastest couplings, 96-97% yield on solid support after 4 min, with tetrazole as the catalyst. The neopentyl phosphoramidite (92)has been prepared and used to make TT-dimers containing a neopentyl phosphorothioate linkage;60 the separated diastereomers were coupled to give oligomers with alternating phosphate and neopentyl phosphorothioate linkages. Two symposia-in-print papers have appeared on the preparation of oligonucleoside phosphorodithioates.61s62The paper by Caruthers et aL61 describes some improvements in the preparation of the preferred monomers, the nucleoside thiophosphoramidites (93); with these improvements, oligonucleoside phosphorodithioates could be obtained in good yields (96-98% per step) with a low amount of impurities (2-3% of monothioate linkages). The same nucleoside thiophosphoramidites (93, R = Me) were used by Gorenstein et al.62, and one of them (B = T) could be obtained pure by flash chromatography on silica under an inert gas. A 12-mer DNA fragment containing one 5'-S-phosphorothioatelinkage has been prepared by tetrazole-catalysed coupling of a standard nucleoside phosphoramidite (94) with a 5'-mercaptooligonucleotide (95).63 3.4 Miscellaneous.- A series of new 2-aminoalkyl diphenylphosphinites (96) has
been prepared and used as catalysts for linear dimerisation of b ~ t a d i e n e sSeveral .~~ phosphinites, e.g (97) and (98), and phosphites (99) were prepared as precursors for chiral phosphine oxides;65the phosphine oxides were made by catalysed Arbuzov rearrangements.
Organophosphorus Chemistry
92
DMTroY (93) NR2 = NMe2,
R
*I
+ HOCH2CHNH2
Ph2P-NMe2
(97) R = Ph,
[
R-S-P+
PhzP-OCH2CHNH2
(99) R = H, Me
(98)
S t
*s
R = Me
-
R
*I
7 [R-S-P=S
.t-
R-P'
S
R = Me, Ph
4:
Tervalent Phosphorus Acids
93
4 Reactions involving Two-co-ordinate Phosphorus The first examples of a two-co-ordinated tervalent organothiothioxophosphine ( 100) have been observed in the gas phase by neutralisation-reionisation mass spectrometry.66 The compounds are formed by the two routes shown from dithioxophosphoranes which are again the primary products of thermal decompositions of Lawesson-type reagents. The haiogenoiminophosphines (101 ) have been prepared from the known chloro compounds by exchange with AgF, MegSiBr, or Me3Sil.67 The crystal structures of (101, X = CI, Br) show that they exist as the Z-isomers.68 A series of aminoiminophosphines (102) were studied with respect to their E/Z geometry.69 The Z-isomer was the thermodynamically stable isomer for .the dimethylamino, diethylamino, and pyrrolidino compound, but (102) with larger N-substituents had the E geometry. Phosphenium ions (103) and 1,2-diimines gave in a facile (1+4) cycloaddition reaction the 1,3,2-diazaphosphoIenium cations (104).70 With two equivalents of imines (105), however, phosphenium ions gave 1,4,2-diazaphosphoIanium cations (106), probably via a stabilised carbocation as shown.71 The 1,3,2-benzazathiaphospholium ion (107) has been prepared as the tetrachloroaluminate, and its crystal structure determined.72 Attempts to prepare the phosphenium phosphaalkenes (108) gave the arnino. ~ ~ stable, diphosphene carbocations (109) which dimerised at room t e m p e r a t ~ r eThe cyclic aminodiphosphene (1 10) was readily formed from 2-phosphinoaniline and tris(dimethylamin~)phosphine.~~ The aminodiphosphene (1 11) formed spontaneously from the phosphinoiminophosphine (1 12) when the latter was prepared as shown.75 The first, stable two-co-ordinated phosphorus heterocycles with only one double bond in the ring, (1 13), were prepared by the simple route shown.76
5 Miscellaneous Reactions Triisopropyl phosphite (114) has been shown to be an effective reagent to convert aldehydes or ketones to hydrocarbons (1 15).77 The mechanism proposed is reminiscent of the Meerwein-Ponndorf reduction of ketones to alcohols. Aminophosphines (1 16) and Lawesson reagents (1 17) gave products (118) at room
94
Organophosphorus Chemistry
' \
(101) X = F, Br, I
(102) NR2 = NMe2, NEt2, NPi2, NBut2, N(SiMe3)2,
+
(Me2N)sP
-
H
4:
Tervalent Phosphorus Acids
R’\
x=c;
95
R2
R’
X
/
N-NH
+
(Me2N)3P
N
+P
NH2
,N-W
(1 13) X = 0, R’ = H, R2 = Ph
X E S , R’ =Me, R2= H
c,
R1, C ,H R2
Me
C :
bJp%
R1\ Me
R2‘
CH,
+
[ O=P-OPri]
Organophosphorus Chemistry
96
S
/
P~'~NH
Ar
-
E
R', P(S-P-NR22)3-, I
Ar
4:
Tervalent Phosphorus Acids
97
temperature where ArPS2 was inserted into one or two P-N bonds.78 The phosphono phosphaalkyne (119) gave an 1,2-addition compound (120) with diisopropylamine and a 1,2,3,44riazaphosphole(121) with mesityl a ~ i d e . ~ ~ Two new cage compounds containing tervalent phosphorus have been prepared. The trithiadiphosphabicyclo(2,2,1)heptanes (122) were obtained by reduction of the corresponding P,P-disulphides with triphenylphosphine,80 and monomeric P2Se5, which has the remarkable structure (123), by CS2 extraction of an annealed amorphous P2Se5 glass.81
References 1 2 3 4 5 6 7 8 9 10 11 12 13 14 15
E. Niecke and D. Gudat, Angew. Chem. lnt. Ed. Engl., 1991, 30, 217. J. Chattopadhyaya (ed.), Nucleosides Nucleotides, 1991, 10, 1. M. F. Wang, M. M. L. Crilley, B. T. Golding, T. Mclnally, D. H. Robinson, and A. Tinker, J. Chem. SOC., Chem. Commun., 1991, 667. S. Jug& M. Wakselman, M. Stephan, and J. P. Genet, Tetrahedron Lett., 1990, 31, 4443. T. Janecki and R. Bodalski, Synthesis, 1990, 799. K. C. Nicolaou, P. Maligres,J. Shin, E. d. Leon, and D. Rideout, J. Am. Chem. SOC., 1990, 112, 7825. H.-L. Eckes, H.-P. Niedermann, and H. Meier, Chem. Ber., 1991, 124, 377. F. Babudri, V. Fiandanese, R. Musio, F. Naso, 0. Sciavovelli, and A. Scilimati, Synthesis, 1991, 225. K. Afarinkia, C. W. Rees, and J. I. G. Cadogan, Tetrahedron, 1990, 46, 7175. R. Yanada, K. Bessho, T. Harayama, and F. Yoneda, Chem. Pharm. Bull. Tokyo, 1991, 39, 1333. T. K. Gazizov, Y. V. Chugunov, and L. K. Sal'keeva, J. Gen. Chem. USSR, 1990, 60, 491. C. Despax and J. Navech, Phosphorus, Sulfur and Silicon, 1991, 56, 105. H. Takeuchi, S. Yanagida, T. Ozaki, S. Hagiwara, and S. Eguchi, J. Org. Chem., 1989, 54, 431. S. V. DAndrea, A. Ghosh, W. Wang, J. P. Freeman, and J. Szmuszkovicz, J. Org. Chem., 1991, 56, 2680. A. A. Prishchenko, M. V. Livantsov, N. V. Boganova, and I. F. Lutsenko, J.
98
16 17 18 19 20 21 22 23 24 25 26
27
28 29 30 31 32 33
34 35
36 37
Organophosphorus Chemistry Gen. Chem. USSR, 1989, 59, 2485. H. Burgess and J. A. Donnely, Tetrahedron, 1991, 47, 111. H. Westermann, M. Nieger, and E. Niecke, Chem. Ber., 1991, 124, 13. H. Vu and B. L. Hirschbein, Tetrahedron Lett., 1991, 32, 3005. 0. I. Kolodyazhnyi, J. Gen. Chem. USSR, 1990, 60, 1541. 0. I. Kolodyazhnyi, 0.B. Golokhov, and S. N. Ustenko, J. Gen. Chem. USSR, 1990, 60, 1536. M.J. Baker, K. N. Harrison, A. G. Orpen, P. G. Pringle, and G. Shaw, J. Chem. SOC., Chem. Commun., 1991, 803. D. J. Wink, T. J. Kwok, and A. Yee, Inorg. Chem., 1990, 29, 5006. S. Kim, M. P. Johnson, and D. M. Roundhill, Inorg. Chem., 1990, 29, 3896. M. S. Balakrishna, T. K. Prakasha, S. S. Krishnamurthy, U. Siriwardane, and N. S. Hosmane, J. Organometal. Chem., 1990, 390, 203. J. T. Mague and M. P. Johnson, Organometallics, 1990, 9, 1254. A. P. Marchenko, G. N. Koidan, G. 0. Baran, A. A. Kudryavtsev, and A. M. Pinchuk, J. Gen. Chem. USSR, 1990, 60, 847. R. V. Davis, D. J. Wintergrass, M.N. Janakiraman, E. M.Hyatt, R. A. Jacobson, L. M. Daniels, A. Wroblewski, J. P. Amma, S. K. Das, and J. G. Verkade, Inorg. Chem., 1991, 30, 1330. A. Alexakis, S. Mutti, J. F. Normant, and P. Mangeney, Tetrahedron: Asymmetry, 1990, 1, 437. E. G. Bent, R. C. Haltiwanger, and A. D. Norman, Inorg. Chem., 1990, 29, 4310. J. M. Barendt, R. C. Haltiwanger, C. A. Squier, and A. D. Norman, Inorg. Chem., 1991, 30, 2342. P. Jacob, W. Richter, and I. Ugi, Liebigs Ann. Chem., 1991, 519. W. Richter and I . Ugi, Synthesis, 1990, 661. S. E. Pipko, Y. V. Valitskii, T. V. Kolodka, A. D. Sinitsa, and M. I. Povolotskii, J. Gen. Chem. USSR, 1990, 60, 849. D. M. Malenko, L. I. Nesterova, S. N. Luk'yanenko, and A. D. Sinitsa, J. Gen. Chem. USSR, 1989, 59, 2347. E. Y. Levina, A. N. Pudovik, and A. M. Kibardin, J. Gen. Chem. USSR, 1990, 60, 663. S. Juge, M. Stephan, J. A. Lafitte, and J. P. Genet, Tetrahedron Lett., 1990, 31, 6357. M. K. Grachev, V. Y. lorish, A. R. Bekker, and E. E. Nifant'ev, J. Gen. Chem.
4:
38 39 40 41 42 43 44 45
46 47 48 49 50 51 52 53 54 55 56 57 58 59 60
Tervulent Phosphorus Acids
99
USSR, 1990, 60, 57. S. Y. Burmistrov, L. K. Vasyanina, M. K. Grachev, and E. E. Nifant’ev, J. Gen. Chem. USSR, 1989, 59, 2360. J. W. Perich and R. B. Johns, Austral. J. Chem., 1990, 43, 1633. J. W. Perich, P. F. Alewood, and R. B. Johns, Austral. J. Chem., 1991, 44, 233. J. W. Perich and R. B. Johns, Austral. J. Chem., 1991, 44, 389. R. L. Pederson, J. Esker, and C.-H. Wong, Tetrahedron, 1991, 47, 2643. W. K. Berlin, W . 4 . Zhang, and T. Y. Shen, Tetrahedron, 1991, 47, 1 . C. Schultz, T. Metschies, B. Gerlach, 6. Stadler, and B. Jastorff, Synlett., 1990, 163. H. J. G. Broxterman, P. A. Kooreman, H. van den Elst, H. C. P. F. Roelen, G. A. van der Marel, and J. H. van Boom, Recl. Trav. Chim. Pays-Bas, 1990, 109, 583. R. Stumpf and P. Lemmen, Z. Naturforsch., 1990, 45b, 1729. N. Hebert and G. Just, J. Chem. SOC., Chem. Commun., 1990, 1497. K. Misiura, I. Durrant, M. R. Evans, and M. J. Gait, Nucleic Acids Res., 1990, 18, 4345. Technical Bulletin 31019, Clontech Laboratories, Inc. Technical Bulletin N 4038, Peninsula Laboratories, Ltd. U. Pieles, B. S. Sproat, and G. M.Lamm, Nucleic Acids Res., 1990, 18, 4355. R. T. Pon, Tetrahedron Lett., 1991, 32, 1715. A. S. Modak, J. K. Gard, M.C. Merriman, K. A. Winkeler, J. K. Bashkin, and M. K. Stern, J. Am. Chem. SOC.,1991, 113, 283. H. Hosaka, Y. Suzuki, H. Sato, S. Gug-Kim, and H. Takaku, Nucleic Acids Res., 1991, 19, 2935. H. Hosaka, Y. Suzuki, S. Gug-Kim, and H. Takaku, Tetrahedron Lett., 1991, 32, 785. T. Wada, R. Kato. and T. Hata, J. Org. Chem, 1991, 56, 1243. T. Wada and T. Hata, Tetrahedron Lett., 1990, 31, 6363. T. Wada and T. Hata, Tetrahedron Lett., 1990, 31, 7461. D. Gasparutto, D. Molko, and R. TtSoule, Nucleosides Nucleotides, 1990, 9, 1087. J. F. Hau, U. Asseline, and N. T. Thuong, Tetrahedron Lett., 1991, 32, 2497.
100
61 62 63 64 65 66 67 68 69
70 71 72 73 74 75 76 77 78 79
Organophosphorus Chemistry G. Beaton, W. K.-D. Brill, A. Grandas, Y.-X. Ma, J. Nielsen, E. Yau, and M. H. Caruthers, Tetrahedron, 1991, 47, 2377. M. E. Piotto, J. N. Granger, Y. Cho, N. Farschtschi, and D. G. Gorenstein, Tetrahedron, 1991, 47, 2449. M. Mag, S. Luking, and J. W. Engels, Nucleic Acids Res., 1991, 19, 1437. H. Masotti, P. G, C. Siv, P. Courbis, M. Sergent, and R. P. T. Luu, Bull. SOC. Chim. Belg., 1991, 100, 63. H. Brunner and W. Zettlmeier, Bull. SOC. Chim. Belg., 1991, 100, 247. H. Keck, W. Kuchen, H. Renneberg, J. K. Terlouw, and H. C. Visser, Angew. Chem., Int. Ed. Engl., 1991, 30, 318. V. D. Romanenko, A. V. Ruban, G. V. Reitel', M. I. Povolotskii, A. N. Chernega, and L. N. Markovskii, J. Gen. Chem. USSR, 1989, 59, 2483. A. N. Chernega, A. A. Korkin, N. E. Aksinenko, A. V. Ruban, and V. D. Romanenko, J. Gen. Chem. USSR, 1990, 60, 2201. L. N. Markovskii, V. D. Romanenko, A. V. Ruban, A. B. Drapailo, G. V. Reitel', A. N. Chernega, and M. I. Povolotskii, J. Gen. Chem. USSR, 1990, 60, 2193. M.-R. Mazieres, T. C. Kim, R. Wolf, and M. Sanchez, Phosphorus, Sulfur, and Silicon, 1991, 55, 147. T. C. Kim, M.-R. Mazieres, R. Wolf, and M. Sanchez, Tetrahedron Lett., 1990, 31, 4459. N. Burford, A. I. Dipchand, B. W. Royan, and P. S. White, Inorg. Chem., 1990, 29, 4938. M. Sanchez, V. Romanenko, M . 4 . Mazieres, A. Gudima, and L. Markowski, Tetrahedron Lett., 1991, 32, 2775. K. Rauzy, M.-R. Mazieres, P. Page, M. Sanchez, and J. Bellan, Tetrahedron Lett., 1990, 31, 4463. A. V. Ruban, V. D. Romanenko, G. V. Reitel', and L. N. Markovskii, J. Gen. Chem. USSR, 1989, 59, 2484. Y. K. Rodi, L. Lopez, C. Malavaud, M. T. Boisdon, and J. Barrans, J. Chem. SOC., Chem. Commun., 1991, 23. G. Olah and A. H. Wu, Synlett., 1990, 54. K. Diemert, G. Hein, A. Janssen, and W. Kuchen, Phosphorus, Sulfur, and Silicon, 1990, 53, 339. U. Fleischer, H. Grutzmacher, and U. Kruger, J. Chem. SOC., Chem. Commun., 1991, 302.
4:
80 81
Tervalent Phosphorus Acids
101
E. Fluck and R. Braun, Phosphorus, Sulfur, and Silicon, 1990, 53, 153. R. Blachnik, H.-P. Baldus, P. Lonnecke, and B. W. Tattershall, Angew.
Chem., Int. Ed. Engl., 1991, 30, 605.
5
Quinquevalent Phosphorus Acids BY R. S. EDMUNDSON
The 11th International Conference on Phosphorus Chemistry was held at Tallinn in 1989. Although many of the papers read there dealt with topics embraced by this chapter, no further discussion on them is included here because of lack of space; for further details, the reader is referred to the extensive Proceedings of the C0nference.l 1.Phosphoric Acids and their Derivatives 3.1.Svnthesis of PhosDhoric Acids and their Derivatives.-Two rather unusual syntheses of dialkyl phosphorofluoridates have been described;these are (a) the reaction between 1,1,2,3,3,3hexafluoropropyl azide and dialkyl hydrogen phosphonates in the presence of triethylamine, when the co-product is CF3CHFCN,2
and (b) the interaction of a dialkyl trimethylsilyl phosphite and perfluoroepoxypropane.3 In addition, a full paper on the transformation of S-trifluoromethylphosphorothioates into phosphorofluoridates (and also of S-trifluoromethylphosphinothioates into phosphinic fluorides) has been published; here, thermolysis of the esters (1) proceeds essentially with retention of configuration. When the reaction is carried out in the presence of triethylamine or CsF, its course is independent of the stereochemistry of the Abbreviations used: Bn = benzyl; Bz = benzoyl; TBPP = tetrabenzyl pyrophosphate; All = allyl; mCPBA = meta-chloroperoxybenzoic acid; LDA = lithium diisopropylamide; HMDS = hexamethyldisilazane; 4DAP = 4-dimethylaminopyridine; DCC = dicyclohexylcarbodiimide. 102
5:
Quinquevalent Phosphorus Acids
X M e 2 N\ 0 -/ y - YR-
R10- *
;:P?5 R
H
(9)a; R = CH20Me
b; R = CH20C2H40Me c; R = CMe20Me
Ar = 2,4-dichlorophenyl
R’O(13)
103
R1O,II
CI’
0 P-ON=C(
R2
CI
104
Organophosphorus Chemistry
starting material. The uncatalyzed reaction is therefore thought to occur through the breakdown of a four-centre transition state (2) whereas the catalyzed process is assumed to proceed via a tbp intermediate such as (3).4 Alkyl 4-nitrophenyl phosphorochloridates have been prepared as intermediates required for the synthesis of phosphate diester anionsr5 and the betaines (4; R = C1 or Ph; X, Y = 0 or S ) have been obtained from the chlorides MeYP(X)RCl and 4DAP.6 Similar compounds have been obtained by the trapping of metaphosphate-type species with 4DAP.7 The phosphoryl chlorides ( 5 ) , obtained from dialkyl chlorophosphites and 1,l-dichloro-1-nitrosoalkanes, have been hydrolysed to the corresponding phosphoric acids, and isolated as their ammonium salts.8 A Perkow reaction between the appropriate P(II1) esters and ethyl bromopyruvate has afforded the phosphoenolpyruvate analogues (6; R1 = R2 = Me2N, R1 = OEt, OPr, or OPri , R2 = Me2N) .g More details have been given of the direct conversion of phosphorous acid into monoalkyl dihydrogen phosphates, and of phosphinic acid into dialkyl hydrogen phosphates, in the presence of an alcohol and through the catalytic effect of copper(I1) chloride; other Cu(I1) salts are ineffective, and the reaction is presumed to proceed through an acid chloride.1° A detailed description has been given for the preparation of the acid (7: R = OH) by the hydrolysis of the acid chloride; enantiomeric forms of the acid have been obtained.ll Cyclic phosphate esters which have been obtained conventionally include the 1,3,2-dioxaphosphepins (7: R = Ar0)12 and the 1,3,2-dioxaphosphocins (8).13 The use of the mixed dialkyl hydrogen phosphonates, (R10)(R20)P(0)H, obtained from (R10)2P(0)H and Ti(OR2)4, allows a conventional synthesis of the triesters (R10)(R20)(R30)P(0)
R ~ O .14 -
from a derived mixed chlorophosphate and
A highly enantioselective procedure for obtaining chiral trialkyl phosphates with 87-91% e.e. involves the treatment of the phosphoramidates (9: Ar = 2,4-dichlorophenyl) with alkoxide anions. This initial step displaces one aryloxy group; subsequent acidcatalyzed alcoholysis then displaces the pyrrolidine moiety from (10) to give a triester (ll), and further similar steps commencing with
5: Quinquevalent Phosphorus Acids
105
the phosphoramidate (10) lead to the chiral triester (12).The study was assisted by knowledge of the chirality of the product triesters and by an X-ray examination of the intermediate phosphoramidate (9a) The e.e. for (11) increases with an increase in the size of the group R in ( 9 ) . The view, (13), along the P-N bond in the phosphoramidates ( 9 ) suggests that sN2(P) approach from the direction
opposite to the pro-(S) ligand (Arlo) is preferred over the alternative, and thus leads to preponderant inversion of configuration at phosphorus.15 The treatment of dialkyl alkenyl phosphates (14) with dimethyldioxiran at below room temperature yields the epoxyalkyl phosphates (15); at room temperature or above, rearrangement to the oxoalkyl phosphates (16) occurs.16 The phosphates (17) are reported to be formed in the reaction between a dialkyl alkenylphosphonite and methyl pyruvate in a 1:2 ratio.17 The cage esters (18; X = 0, S , or Se) have been prepared in attempts to control the geometry around a central phosphorus atom, and in particular to generate and stabilize a rectangular-pyramidal geometry.18 Much of the reported synthetic work related to derivatives of phosphoric acid is concerned with biologically important compounds and their synthetic analogues; in much of the work, phosphorylation has been achieved through the application of phosphitylation reactions between the hydroxylic compounds and a phosphorus(II1) amide in the presence of 1,2,4-triazole or tetrazole, and followed by oxidation with t-BuOOH or mCPBA, and the methodology is proving to have a wide scope with practically unlimited variation in phosphitylation reagent. Thus, a neat synthesis of symdihydroxyacetone monophosphate (20) starts with the diol (19)(Scheme 1) which is phosphorylated using dibenzyl diethylphosphoramidite as the initial reagent.19 Aziridine-2-carbonitrile serves as a perhaps surprising precursor to 0-phosphoseronitrile (21) and thence of glycolaldehyde phosphate (Scheme 2). The inverse addition of the carbonitrile to phosphoric acid yields (21) and careful hydrolysis of this affords the glycolaldehyde as the monohydrate (22) through a retro-Strecker reaction. The inverse treatment of (21) in MeCN with
106
Organophosphorus Chemistry
0
0
II
(R10)2P-OHR4
n
c
R2 0 R3
c r. t.
(Et0)zPCR =CH2
R = H or Ph
0
+ -
:‘c-0’
CRzCH2
MeCOCOOMe D
(EtO)
Me’
Me
‘COOMe
X
I
II
OH
!
I
MeCOCOOMe
Me
R I
(Et0)2P-O-C-CH2-C=C, I
COOMe
,
-
t
~
i,~ii
~
5’
(1~9) R =~ (BnO),P ~
RO
Reagents:
II
(R10)2P-0 R3 R22 R 4
t
iii,iv
i, (Bn0)2PNEt2,tetrazole; ii, 30% H202; iii, Pd/C, H2, EtOH; iv, H30+, heat
Scheme 1
-
,COOMe Me
0 H O A O P O 3 H 2
5:
107
Quinquevalent Phosphorus Acids
Reagents: i, H3P04, heat; ii, H20, heat; iii, NH40H; iv, CF3S03H, 80 "C, MeCN
Scheme 2
J
iii
OH
O R:p: :$
II OH
0-P,
0 Reagents: i, 13noP(NEt~)~, tetrazole, MeCN; ii rn -CPBA; iii, ROH; iv, H2, PdK, EtOH Scheme 3
B n O A O H
(25)
,OR
6 OBn
108
Organophosphorus Chemistry
trifluoromethanesulphonic acid yields (23) and thence the monohydrogen phosphate (24).20 Phosphitylation methodology has been used to phosphorylate N-protected serine,21122 leading to the preparation of 0phosphoserine-containing peptides,23 a topic which has been reviewed.24 Peptides containing O4-phosphory1ated-L-tyrosine have been obtained following the phosphorylation of N-Fmoc-L-tyrosine using the same procedures.25 The considerable interest shown during recent years in the synthesis of phosphates of myo-inositol has continued. Nine (i.e. all) inositol diphosphates and 11 (out of 12) inositol triphosphates have been identified in the chemical hydrolysate of phytic acid.26 One synthesis of myo-inositol monophosphate monoesters is based on the ring opening, by alcoholysis, of the 1,3,2dioxaphospholane ring whose formation depends, in turn, on the availability of vic-hydroxyl groups (Scheme 3). Based on the reactions in Scheme 3, the tetra-O-benzyl ether (25) was converted, through the monobenzyl monoalkyl esters (26; R = Bn) and ( 2 7 ; R = Bn) (the product ratio of which depends on experimental conditions) and their hydrogenolysis into the monophosphate monoalkyl esters (26; R = H) and (27; R = H).Z7 A conventional conversion of DL-(28) into (30) via (29) thereby provides a route to the 6-O-(2-aminoethyl)-DL-myo-inositol l-phosphate (31) and the cyclic monohydrogen phosphate (32); the latter is an analogue of an inositol phosphate potentially important in connection with the mode of action of insulin.28 4-0-(2-Amino-2deoxy-1,D-glucopyranosy1)-D-myo-inositol l-(dihydrogen phosphate) and the analogous .r,D-galactopyranosyl-D-chiro-inositolphosphate may have a similar function; the inositol moieties for these have been synthesized from the stereoisomeric 1,2:4,5-di-O-cyclohexylidene-DLinositol O-benzyl ethers, (33; R = Bn) and (34; R = Bn) respectively, by sequential camphanoylation, resolution, debenzylation, phosphorylation (by phosphitylation using dibenzyl NN-diisopropylphosphoramidite), and decamphanoylation (MeOH, NH3); the enantiomers of each of (33; R = P(O)(OH)2) and (34; R = P(O)(OH)2) were obtained.29
2,3,4,6-Tetra-0-benzyl-myo-inositol (35; R = Bn), also resolved through the l-O-camphanoates, has been phosphorylated (using
109
5: Quinquevalent Phosphorus Acids
(28) X = OTS-p (29) X = N3 (30) X = NH2
‘OBn
OH
(35)
(34)
OSiEt,
“OSiEt3
H203PO’*
R20
HO (37) R’ = BZ (40) I?’ = H
(38) R’ = Bz R2 = CsHd(CH20)2P(O) (41) R’ = H R2 = CeH4(CH20)2P(O)
OP03H2 (39) R’ = H (42)
R’ = PO3H2
Reagents: i, ( 3 6 ) ,tetrazole, CH2CI2;ii, rn -CPBA ; iii, H2, Pd/C, MeOH
Scheme 4
110
Organophosphorus Chemistry
di(2-cyanoethyl) NN-diethylphosphoramidite) and the product hydrolysed (0.2 M NaOH aq.) and hydrogenolysed (H2, Pd/C) to give Dmyo-inositol lt5-bis(dihydrogen phosphate) (1,5-IP2) and its Lenantiomer (~,~-D-IPz).~O The 1,4,5-IP3 was prepared in a similar
manner starting with 1,2,4-tri-O-benzyl-myo-ino~itol.~~ A synthesis of the same compound by Russian workers has also been reported, resolution being achieved through the use of a D-mannose ortho ester.32 Yet a third procedure for the preparation of the same compound used the benzodioxepin (36) as the phosphitylation agent. The last steps (Scheme 4) utilized the bis(triethylsily1) ether (37) and its conversion into (38) followed by hydrogenolytic removal of protecting groups to give lI4,5-IP3 (39). 1,3,4,5-IPq was similarly
prepared from (40) via ( 4 1 ) . ~A~ modified phosphitylating agent allowed the ready synthesis of a myo-inositol monohydrogen phosphate 4,5-bis(dihydrogen phosphate) as its 1-0-(3-aminopropyl) ester (43; Scheme 5).34 Other eaminoalkyl esters of various inositol phosphates have been reported.35 Some corrections have been made to previously published data on the total synthesis of myo-inositol polyphosphates.36 Following reaction with 2,2-dimethoxypropane, various monoand di-O-isopropylidene derivatives of phosphatidylinositols have been obtained from yeast fractions; they were evidently useful as starting materials for further phosphorylations.37 The syntheses of various deoxy-myo-inositol phosphates have been reported. Quebrachitol (44) was the starting material for the preparation of D-3-deoxy-myo-inositol lI4,5-tris(dihydrogen phosphate)(47) and the 1,5,6-triphosphate isomer (48)(Scheme 6). Several steps were required to convert the quebrachitol into the precursors (45) and (46).38 The same workers also prepared optically active 3-deoxy-3-fluoro-D-myo-~nos~tol1,4,5-tris(dihydrogen phosphate) (50) via (49), also starting from quebrachitol.38 2-Fluoro2-deoxy- (54) and 2,2-difluoro-2-deoxy-myo-inositol 1,4,5tris(dihydrogen phosphate)(55) were prepared from (51) via (52) and (53), respectively; as in Scheme 6 phosphorylations were here performed using TBPP.40 The epoxide (56) was the starting material for a synthesis of the 2~,4~-dihydroxy-lp-phosphoryloxycyclohexanes(57), potential inhibitors of inositol monophosphatase, and their isomers (58)(Scheme
5:
111
Quinquevalent Phosphorus Acids OBn
OBn
-
i, ii
"'OBn
o + ~ '-'OH ' 'OOP03H2
NHCbz
'"OBn OP03H2
~ H3+ o ~
H~o~Po***
(43)
Reagents: i, BnO(Pri2N)POCH2CH2CH2NHCbz,tetrazole; ii m -CPBA; iii, 0.1 M HCI; iv, (BnO)2PNPri2, tetrazole; v, H2, Pd/C, EtOH
Scheme 5
H O . OH , - p H MeO'**
RQ
several steps
'-'OH
BzO'-'
"OBn
HO
BzO
(44)
(45) R = H (49) R = F
yraloEE steps
Bz
OEE
RQ
i - iv
OP03H2 (47) R = H (50) R = F
- iv
Bn0'OBz
OP03H2
EE = ethoxyethyl Reagents: i, K2CO3, MeOH, r.t.; ii, NaH, TBPP, DMF, 0 "C; iii, H2/Pt02,EtOH; iv, H20, r.t.
Scheme 6
P03H2
H203 ~ 0 ' ~ - "OH
OH i
OH
D
N
0rgun op h osp horus Chemistry
112
(54)X = H
(52) X = H (53) X = F
(55) X = F
v, vi
i, ii or iii
or vii + viii + vi D B n oBnO 6 - = R
BnO
R = BnO,
(56)
Po'
OH HO
(57) R = HO, r
M e y , o r C N
O
-
o r Me(CH2)c
F!
F! or vii, viii, vi
OH (58)
BnO
Reagents; i, ROH, A1203, toluene, heat; ii, E t 2 A I C 3 X toluene, 0 "C; iii, Et2AICN, toluene, 0 "C; iv, R2CuLiCN, Et20; v, NaH, TBPP, THF; vi, H2, Pd/C, EtOH aq.; vii, (Bn0)2PNEt2,tetrazole, CH2C12, r.t.; viii, m -CPBA, CH2C12,-78 "C;
Scheme 7
9
5:
Quinquevalent Phosphorus Acids
113
7).41 Some closely related compounds have been prepared for use in affinity chromatographic work; the acids (59; R = H) and (60; R = H) with Z = NHCH2CH2NH2 (a function allowing attachment to Sephadex 4B following treatment with CNBr), are obtained by hydrogenolysis (H2, Pt02) of (1RSt3RS,4RS)- (59; R = Ph) or (1RS,3SRt4SR)- (60; R = Ph)
methyl. trans-3,4-bis[(diphenoxyphosphinoyl)oxy]cyclohexene1-carboxylate, in turn the result of phosphorylation (diphenyl phosphorochloridate, pyridine) of the oxidation products from 3cyclohexen-1-carboxaIdehydehyde.42
Descriptions have been given of the preparation of phospholipids (61) by phosphitylation of a 2,3-bis(acyloxy)-propanol with a cyclic phosphoramidochloridite (Scheme 8; route a)43 and of sulphur-containing analogues (Scheme 8; route b)44 using ethylene chlorophosphate as phosphorylating agent, as well as of the phosphorylcholine analogues (62; E = N, R2 = Me; E = P, R2 = Me, Pr, or BU) . 4 5 The interaction of diazoacetic esters and dialkoxyphosphinoyloxosulphenyl chlorides produces 0,O-dialkyl S(alkoxycarbonylchloro-methyl) phosphor~thioates,~~ and the treatment of a range of 0-propynyl phosphorothioates and phosphoramidothioates (63) with HgS04 brings about not only thione-thiol isomerization but
also a prototropic change to the S-allenyl esters (64).47 The reaction between phosphorothioites or related esters and ethyl bromopyruvate produces sulphur-containing analogues of phosphoenolpyruvate; thus (65) yields (66), and (68) is obtained from (67).48 The condensation between a reducing monosaccharide and a phosphorothioic acid dialkyl ester under phase transfer conditions is aided by TsCl to provide 0-glycosyl phosphorothioic esters; the nature of the quaternary salt in the system governs the d/f ratio of the p r o ~ ? u c t s . ~ ~ Yet another phosphitylating agent was used in the synthesis of DL-myo-inositol dihydrogen phosphorothioate (71) from racemic 2,3,4.5,6-penta-O-benzyl-myo-inositol (Scheme 9). The separate D and L forms were obtained in the same way from the resolved forms of (69).50 Other workers have used similar methodology to obtain the 1phosphorothioate 4,5-diphosphate (73), an unusual feature of the
114
Organophosphorus Chemistry
+
(b)
CI-P,
R3 = Me3Si
0
XR3
x=s
4
X = 0,R3 = H, [N,P-CI 1
Me
ii
--.:“)
R’O+
iii, iv
N Me
f
R 2 0 i
x-7-0 -0
(61) X = 0 or S
Reagents; i, Me3N; ii, Et3N or Py. ; iii, 4 -O2NC,H4/O“CGH,Me iv, Me2S04, H20
Scheme 8 0 -0.11 P-0CR3=CHCH2lh2, R’O’
R’O,
5s
R’O,
R20pbCH2CECH
(63)
R2’
50 P ‘SCH=C=CH2 (64)
R’ = Me, Et, Pr, Pr‘, Bu’; R2 = NH2 R” = Me; R2 = NHR3; I?= Me, Pr, Pr’, etc.
(65) X = OR’ (67) X = SR
bhMe3
(66)X = OR” (68) X = SR
- 4;
5:
Quinquevalent Phosphorus Acids
115
"OBn BnO
O/\/CN
iii
"OBn
(70) X = S -
iv - vi
BnO
OH
(70) X = lone pair
(711
Reagents: i, Pri2NP(OCH2CH2CN)CI,Pri2NEt, CH2CI2;ii, HOCH2CH2CN, tetrazole, MeCN; iii, '/&, Py. ; iv, MeOK, MeOH; v, Na, NH3(I); vi, Arnberlite resin IR 118
Scheme 9
i
HO'-
'"OBn
(72) R' =CH=CHMe
ii iii iv
"OBn
HO (72) R' = ally1
0
0PO, '"OBn
0
vi
0yR2)2
"'OH
(73)
0
Reagents: i, (Ph3P)sRhCI, triethylenediarnine; ii, (R20)2PNPr\, tetrazole, CH2C12; iii, Bu'OOH; iv, HgO/HgCI2, Me2CO; v, l/&-Py. ; vi, NH3(1), Na
Scheme 10
s2-
116
Organophosphorus Chemistry
reaction sequence (Scheme 10) being the use of the ally1 group for protection purposes and the manner of its removal.51 Some of the complexities of the reactions between P4S10
and alcohols have again been examined through the use of P-31 nmr spectroscopy.52 Dithiophosphoric acids derived from 1- and 2hydroxyadamantane have been described.53 Cyclic phosphorodithioic acids have been converted into S-Ge(IV)54 and S-Sb55 derivatives. Organoselenium (74)56 and organotellurium (75)57 derivatives of acyclic and cyclic phosphorodithioic acids (as well as of phosphonodithioic acids) have been prepared by the interaction of th chalcogen (IV) halide and a metal salt of the acid, or from the free acid with R3TeOMe or R2Se(OEt)2. The acid (76; R = SH) and some of
its derivatives (76; R = C1, Br, alkoxy, amido) have been obtained from racemic or (R)-2 ,2'-dihydroxy-l ,1'-binaphthyl.58 59 0-Dithiophosphorylation of the hydroxyamino carboxylic acid tyrosine, serine, and threonine protected at nitrogen (boc) and carboxyl (di-p-tolyl ester) is achieved using S,S-diphenyl phosphorodithioate anion in the presence of isodurenedisulphonyl dichloride together with tetrazole in pyridine.60 A useful tabulation of data on chiral esters and amides of phosphorothioic, phosphorodithioic, phosphorotrithioic, and phosphoroselenothioic acids, has been published. Examples of the reactions used to obtain these compounds are illustrated in Scheme 11; they involve the use of enantiomers of 1-phenylethylamine, followed by cleavage of the P-N bond by treatment of the amide anion with CS2 and methylation (MeI), a process occurring with retention o I
configuration at phosphorus. Typical final products are the esters (78), (79), and (81), obtained via the thioamides (77) and (80).61 Treatment of the diazoles (82; X = N or CH) with phosphoric anhydride yields not only the phosphoramidic acids (83) but also the anhydrides (84).62 The simple transformation of N-propynylphosphoramidates into 3-(phosphorylamido)propanoic acids (Scheme 12),63 and the synthesis of the diethylphosphorylformamidines (85)64 have been effected in the ways indicated. Some attempted syntheses of phosphorus-containing cryptands from (S)P(NMeNH2)3 have proved unsuccessful.65 Reactions between P4S10 and 2-aminobenzamides have provided examples of the system
5: Quinquevalent Phosphorus Acids
117
Reagents: i, (S)-PhCHMeNH2; ii, Se; iii, Mel; iv, NaH, CS2; v, EtOH, AgNO3; vi, Etl; vii, Prl Scheme 11
Organophosphorus Chemistry
118
R2 = H or NO2 R2
R’ (82) R’ = H (83) R’ = PO3H2 (84) R’ = P(O)(OH)OP(O)(OH)2
?
(R’O)2PNR2CH2CECH
-
ii
?
(R10)2PNR2CH2CZCSi Me3
?
1
iii - v
( R’0)2PNR2CH2CH2COOH
THF; Reagents: i, BuLi, THF, -78 “C; ii, Me3SiCI,-78 “C; iii, HB(C6H11)2, iv, H202, NaOH; v, H30+
Scheme 12 0
-
II
(EtO)*PN=CHOEt
CGH6
0
S
X A
nruru2
i
II
(Et0)2PN=CHNR’R2
ii
I I /CI Arur, A..firn
N.NH,
+
X I10SCH2COOEt ArOP, N.NH2
(87) Reagents: i, MeNHNH2; ii, NaSCH2COOEt, MeCN; iii, MeCN, reflux
Scheme 13
EtOH
(85)
X
*
+
5: Quinquevalent Phosphorus Acids
119
(86), some reactions of which will be referred to later.66 Cyclic phosphorothioic hydrazides in the form of 2-aryloxy-3-methylhexahydro-1,3,4,2-thiadiazaphosphorin-5-one 2-oxides and 2-sulphides (87) have been prepared as indicated in Scheme 13.6’
.
.
~eactinnsof phmghzric k Further examples of the base (LDA) catalyzed rearrangement of
1.2.
phosphoryl groups attached to oxygen bonded to aryl dysterns have been reported, this time in the naphthalene series. Thus diethyl 1-naphthyl phosphate yields diethyl (1-hydroxy-2-naphthy1)phosphonate, and diethyl 2-naphthyl phosphate affords diethyl (3-hydroxy-2-naphthy1)phosphonate. Tri-1-naphthyl phosphate gives tris(1-hydroxy-2-naphthy1)phosphine oxide, and in general (88)
affords (89). 6 8 In contrast to the ready rearrangement of diethyl phenyl phosphate, even at -1004, aryl phosphorodiamidates (90) are effectively o-lithiated by EtMeCHLi in THF at the same temperature, and the species can be trapped by reaction with elecpophiles such as MegSiC1, MeI, or carbonyl compounds. However, at -78 the
phosphoryldiamido group migrates rapidly and regiosele~tively.~9 The stereochemistry of the same rearrangement in the 1,3,2oxazaphospholidine series has also been examined. Using an inseparable mixture of the (2R) and ( 2 s ) compounds (91) and (92) in the ratio 95:5 and derived from pseudo-ephedrine, the rearranged (LDA, THF) material, isolated in 38% yield, corlsisted of only one component (93) of (2R,4S,5S) configuration. On the other hand, the (2S,4R,5S) and (2R,4R,5S) diastereoisomers, derived from ephedrine, were separable; the action of LDA on the former produced 34% of ring opened product and only 14% of a compound in which the ring was retained, whereas the latter stereoisomer, possessing the least congested system with ArO trans to cis Me and Ph groups, afforded 85% of a product in which the ring was retained as was the stereochemistry at phosphorus.70 In the base-catalyzed hydrolysis of the acyl phosphate (94), Cu(II), Ni(II), Co(II), and Zn(I1) ions have a pronounced rate increasing effect, by a factor of up to 107; the effect of Mg(I1) ions is less pronounced, the difference being a factor of 104.71 A detailed study of the displacements within diphenyl 4-nitrophenyl phosphate by aryloxide anions reveals results consistent with a
120
Organophosphorus Chemistry
OMe
OMe
(94)
(b)
Me Me H
(c)
H
Me Me
H, 4-Me0, 4-NO2, 2 +(Nod2 H, 4-NO2
5: Quinquevalent Phosphorus Acids
121
mechanism involving either a single transition state or a two-step process with two reactive intermediates, for formation and breakdown, with almost identical transition states. For the displacement by 4nitrophenoxide the vvsymmetricalreactionvvis slightly unbalanced, and bond formation does not keep up with bond fission in the transition state which thereby acquires some phosphorylium ion character. The transfer of the diphenyl phosphoryl group is thought to proceed through an intermediate species having less tbp character than that for the transfer of the diethyl phosphoryl moiety.72 I7O Nmr spectroscopy has been applied in a study of the alkaline hydrolysis of a series of cyclic phosphate esters (95) in the 1,3,2-dioxaphosphorinane series. Following the hydrolysis step, using aq. NaOH containing H2170, the product(s) were methylated (diazomethane). In all cases the ring appeared to be retained, and the distribution of hydrolysis products, obtained by exo hydrolysis through either retention or inversion (Scheme 14), was determined by analysis of the spectra, there being significant differences in the 170 chemical shifts for singly and doubly bonded oxygen, and for axial and equatorial oxygens.Through the series (95), the retention/inversion ratio varied from 1:l to 3:l. For Ar = Ph or 4MeOC6H4 the predominant reaction was retention of configuration, but
for the 4-nitrophenyl compounds there was slight predominant inversion. The results were rationalized by postulating that the direct displacement with inversion competes with pseudorotation in P f V ) intermediates leading to retention of configuration.73 Under alkaline conditions in aqueous alcohols ROH, loss of aryloxy groups from diary1 N-arylphosphoramidates occurs by an sp.~2(P) process rather than by an ElcB mechanism judging from the steric effects on increasing the size of the group R.74 In connection with the design of phosphitylating agents for the 0-phosphorylation of aminohydroxycarboxylic acids and of the peptides derived from them, studies have been made of the stability under acid conditions of dibenzyl isobutyl phosphate itself and also of Ar-substituted dibenzyl isobutyl phosphates (96; X = H, F, C1, or Br) derived from the phosphitylating reagents (97) and (98) and isobutanol in the presence of tetrazole, followed by oxidation with mCPBA.22 For the parent dibenzyl isobutyl phosphate, treatment with 4M HCl/dioxan or 50% trifluoroacetic acid in dichloromethane, results
122
Organophosphorus Chemistry
(97) R = Et, X = H or Br (98) R = Pr’, X = F or CI
5: Quinquevalent Phosphorus Acids
123
in predominant loss of the benzyl groups; this process assumes a minor significance in reactions with 1M HC1 in acetic acid. In the synthesis of 0-dibenzyl phosphorylated tripeptides, the use of either 98% formic acid or 1M HC1 in acetic acid to remove N-protection (Boc) is satisfactory. For the halogenated dibenzyl isobutyl phosphates, the di-4-bromo compound has the greatest stability in formic acid or 1M HC1 in acetic acid, and the 4-bromobenzyl group is the group best suited for protection purposes in the acidolytic removal of boc protection in such cases.22 It has been observed that, during long periods (1 - 4 years), the peptides ( 9 9 ; R = Bn) afford H-Ser.NHMe as salts with dibenzyl hydrogen phosphate. A possible explanation lies in an 0 to N migration of the dibenzyl phosphoryl group through a P(V) intermediate followed by loss of the N-Ac group, and fission of the P-N bond by acidolysis.75 A study has been made of the reactions which take place between epoxides and metaphosphates or related species.76 The metaphosphate species were obtained by the thermolysis of appropriate compounds based on the 2,3-oxaphospha[2.2.2]octane structure, a procedure recently reviewed.77 The reactions between the epoxides (104; R2 = Me, t-Bu, Ph, CH2Br, or CH2OMe) and ethyl metaphosphate
(103)(from 100) yielded stereoisomers of the 1,3,2-dioxaphospholanes (105; R1 = EtO, X = 0). Three possible mechanisms for the reaction were considered and although two of these seemed unlikely from theoretical considerations, the slight positive evidence for the third, involving an enol phosphate, was not considered sufficient to positively characterize this mechanism as the one operating.The reaction of (103) (from 101) with (104; R2 = Me) also proceeded to give a mixture of diastereoisomeric 1,3,2-dioxaphospholanes (105; R1 = EtzN, R2 = Me, X = 0). However the final product from (102) was
a mixture of the diastereoisomers of (106) and (107)(R1 = EtO, R2 = Me, X = S ) and the corresponding (105) was absent. Interestingly, the same ratios of stereoisomers and regioisomers of products were obtained from 2-methyloxiran and 0,O-diethyl phosphorothioate as from the metathiophosphate. Available evidence would seem to indicate that a similar reaction involving a methyloxetane yields stereoisomers of an analogous 4-methyl-1,3,2-dioxaphosphorinane 2-0xide.~~
124
Organophosphorus Chemistry
A somewhat novel reaction leading to phosphoric amides or to phosphonic amides, consists in the displacement of alkoxy groups from trialkyl phosphates or dialkyl alkylphosphonates by Ti(IV)(NRz)nC14-, or M ~ ( N E ~ z ) ~ . ~ ~
The cyclic phosphoric acids (108; R = H or halogen) have been synthesized and their potentiality as resolving agents explored.79 The 2-chlorophenyl-substituted acid can resolve ephedrine whereas (108; R = H) cannot. A second chlorine atom introduced into either the remaining ortho position, or the para position, increases the resolving ability: the latter appears to be related to the enthalpy of fusion. The crystal structures of pairs of diastereoisomeric salts have been analyzed in some detail.80 2,2f-Dihydroxy-l,lt-binaphthyl has been resolved in a new, efficient process in which the racemic cyclic phosphorochloridate (7; R = Cl) is converted into the amide using (S)-(-)-2-phenylethylamine, and the resolved amides reduced directly to the diol with LiA1H4.81 In an alternative procedure, the resolved methyl phosphate (7; R = MeO) is reduced with Red-A1 with retention of configuration.82 The chemistry of lIl'-binaphthyl-2,2'-diyl hydrogen phosphate, including its use as a resolving agent, has been reviewed.83 Photolysis of dialkyl benzyl phosphates (109) in solution in an alcohol R20H affords mixtures of the two ethers (111, 112) and the bibenzyl (112). For the diethyl esters (109; R1 = Et) in t-butanol, the main product is the ether (110) accompanied by the ethyl ether (111) and the bibenzyl. Using diethyl (S)-(-)-l-phenylethyl phosphate in BuOH, the main product, i.e. butyl l-phenylethyl ether, showed a small net retention of configuration whilst the recovered phosphate ester was 28% racemized. Evidence based on l80 scrambling and substituent effects on reaction rates favoured an intermediate benzyl cation-phosphate ion pair.84 In the presence of potassium carbonate simple dialkyl chlorophosphates and chlorothiophosphates act as alkylating agents on nitrogen or sulphur for tautomeric N=C-SH/HN-C=S triad systems in thiazoles.85 LDA, normally considered a strong base, although weakly nucleophilic, nevertheless behaves as a strong nucleophile towards 010-diethyl S-phenyl phosphorothioate,and attacks the hard P=O centre to give diethyl NN-diisopropylphosphoramidate; no reaction occurs
125
5: Quinquevalent Phosphorus Acids
E
(EtO),PSCH,CONMeCOOEt (1 15)
E
E
(EtO),PSCH,P(OEt)2 (1 16)
EtO, //x /p\ EphO R (117) R = OH, X = S (118)R=H, X = O
(119)R=OH, X = S (120) R = H, X = 0 (121) R = PhO, X = S (122) R = EtS, X = S
126
Organophosphorus Chemistry
with diisopropylamine itself. A reaction between the same phosphorothioate and a Grignard reagent RMgX yields the phosphonate (EtO)2P(0)R, and also (Et0)2POMgX, together with PhSMgX and RSPh.B6
In the alkaline hydrolysis of S-butenyl thiophosphates (113 X = H, C1, C1, or N+Me3) the nature of the substituent X appears to
control, to some extent, the reaction pathway.87 Alkaline hydrolysis of chloromephos (114) and mecarbam (115) involves attack by HO’ at phosphorus with P-S bond cleavage; at the S-Me carbon atom with C-S cleavage; or, in the case of (115), at the carbonyl carbon atom with C-N bond fission. Initial hydrolysis of the carboxylic ester group from (115) is not observed, but unusual reactions in the case of (114) include S-alkylation of 0,O-diethyl phosphorodithioate anion to give theO,O,S-triethylester; attack of the anion on the starting material to give a trithiopyrophosphate; and at the chloromethyl carbon to give (116).88 The oxidation of triester phosphorothioates and diester phosphorodithioates with magnesium monoperoxyphthalate in water give up to 70% dialkyl hydrogen phosphonate; a mechanism for the process has been advanced (Scheme 15).89 For the individual diastereoisomers of the diesters (117) and (119), the reaction proceeds with ratentio of configuration to give the products (118) and (120), and with inversion of configuration for the triesters (121) and (122). In non hydroxylic solvents the intermediate (123) collapses with the expulsion of sulphur; otherwise oxidative activation of the thiophosphoryl bond is followed by attack at phosphorus by solvent with subsequent loss of substituent followed by further oxidation at sulphur.90 In another study, the formation of pyrophosphates from the oxidation of 0s-dimethyl phosphoramidothioate in non-aqueous media (absence of nucleophiles) has been stressed (Scheme 16).91 A new study, employing P-31 nmr spectroscopy in particular, has examined the behaviour of chlorine, bromine, iodine, and sulphuryl chloride on the sulphur-containing triesters (126).92 [For results pertaining to analogous phosphonic triesters see Section 2.2 Previous studies on the chlorination or bromination of phosphinothioic esters have already been summarized (Organophosphoru Chemistry:1988, 19, 170; 1991, 23, to be published)]. When (126a) was treated with sulphuryl chloride in dichloromethane at about -70 , the nmr signals suggested the presence of (130; Y = S02C1), a decision
[
5: Quinquevalent Phosphorus Acids
[OI
S II
(R10)2pS]
H2;)
~
[
127 R1o‘~-S-OH] OMH
R’O’
( R’O)2P-R2
Scheme 15
t
PI
MeO-P-SMe I
-
0
0
r\
II
MeS-P-OMe
MeO-P-0-SMe I
NH2
NH2
(1 24)
0 II MeO-P-OH I
+
t
MeSOH
MeO-7-0-
+
MeO-PLSMe I
NH2
NH2
/(I241 (125)
+
MeSOH
MeSOSMe + H20
E
E
MeO-P-0-P-OMe I
NH,
1
NH2
(1 25)
Scheme 16
+
MeSSMe
128
Organophosphorus Chemistry
?
(Me3C.CH20)2POP(OCH2CMe3)2 (139)
(134)
(135)
Forall : (a)
(b)
(c) (d)
R' M83CCH2 Et Pr Me
(Me3C.CH20)2P(S)SSP(S)(OCH2CMe3)2 R2
R'O
R3 Me
R'O R1O But
Me Me
Et
Scheme 17
(140)
5:
Quinquevalent Phosphorus Acids
129
reached following an independent synthesis of (130; Y = C1) from (139) and MeSC1. By contrast to results described in earlier papers, there were no nmr signals for (128; X = C1, Y = SOzCl), and it would therefore appear that this converts into [130;Y = cl(c13) or SO2ClI
and /or (129; Y = C1) i.e. it Actually, (128) does not give to -50'. The reaction between that with sulphuryl chloride, (127)/(128)(X = C1, Y = C1 or
is removed as fast as it is formed. rise to (129) but rather to (130) at up (126a) and chlorine is much faster than and (129; Y = C1) is formed from Cl3) via pathway (A) in competition
with routes (B) and (C). The relatively high nucleophilicity of C1(compared with that of the chlorosulphonyl anion) would cause the decomposition of (130; Y = C1 or C13) more rapidly giving monophosphorus products, and in fact, the substance was not observed at above -50: Apart from unreacted starting material , the products at -80'' were (130; Y = C1 or Cl3) and (129; Y = Cl). As the reaction
temperature was raised the amounts of (126a) and (130) decreased to leave only (129) together with some (138). The reactions of (126b,c) gave the corrresponding (130) at -8d'to -50', but the yields of (129) were lower than from (126a) and some side-products (135) and (136) were produced presumably by attack of Y- on carbon attached to oxygen. The phosphonium salt (130c: Y = Br or Br3) was the main
product from (126a) and bromine in dichloromethane; it is stable to +loc but decomposes at room temperature to give 6% (129b), 10% (137a)(by attack of 'Y on carbon attached to sulphur), 13% (136a), 20% (138a), 15% bis(2,2-dimethylpropyl) hydrogen phosphate, and 7% of the disulphide (140). The reactions between (126 a,b,c) and iodine in dichloromethane were all much slower, and the products were not identified.92 Reactions between salts of 0,O-diethyl hydrogen phosphorodithioate and N-benzyltrifluoroacetimidoyl chloride (141) or the isomeric compounds (142) and (143) have been described.93 In benzene, and in the absence of a strong base, the initial product from (141) comprises the equilibrium mixture of (144) and (145), evidently stable at room temperature, and not undergoing a 1,3hydrogen shift even on warming. However, in the presence of 1,4diazabicyclo[2.2.2]octane, the irreversible isomerization of the mixture into (146) occurs in chloroform at room temperature. The
Organophosphorus Chemistry
130
I
S II
- F3CCHZNCPh
F&CH2N=CPh
- F&CHZN=FPh
SP(S)(OEt)2
(149)
hv
c
Q
]
0 II
“N-PR,
-Q-!R2 -N
R‘R~P(X)NI+
(R’0)2P-NH-CR2
!
V
(155) a X = Y = S b X=O,Y=S
c X=S,Y=O d X=Y=O
CI,CCH=NAc
I
R1R2P(X)NHCSF?
R’ R ~ P -N=
!
(156)
c-SCHNHAC I
R3
I
CCI3
-
X
RW~NH~HNHA~
cc13
5: Quinquevalent Phosphorus Acids
131
product from (142) i.e. (147), also undergoes a phosphorotropic shift to (148) in the presence of triethylamine in boiling toluene; prototropy then affords (149) obtained, in equilibrium with (150), by reaction of the phosphorothioate salt with (143). The interaction of (141) with ammonium 0,O-diethyl phosphorothioate affords a phosphorotropic mixture of the S-phosphoryl analogue of (144) and the phosphoryl analogue of (145) which converts slowly into the Sphosphoryl analogue of (146). In summary, the ease and mode of migration of a P=X species in the triad S-C-N is highly dependent on X and other groups. 1,3-Hydride shifts in the C-N-C triad depend to a lesser extent on substituents on phosphorus, and they occur less readily than phosphorotropic shifts. Thus, the transfer of a hydrogen atom from the benzyl group to the imidoyl carbon is irreversible and requires the presence of a basic catalyst.93 N-Phenylphosphoramidates are readily converted into phosphoric acid salts when treated with sodium or tetrabutyl-ammonium nitrite in acetic anhydride.94 The rearrangement of (151) into (152) is catalyzed by TmsC1, BzC1, or TsC1.95 That of (153; R = E t O , PhO, or Ph) into the corresponding (154) is photocatalyzed.96 Hydroborations of dialkyl N-alkyl-N-propargylphosphoramidates have been carried out.97 The compounds (155) possess three active reaction sites, on N, X, and Y. The salts of N-phosphorylated derivatives of thiobenzamide as well those of N-phosphorylated thiobenzamides themselves are alkylated at P=X ( X = 0 or S ) to give monophosphazenes; alkylation at N does not occur.98 The heterocyclic compounds (86; R2 = R3 = H) are methylated (Me2S04, H O ' ) to give a mixture of the methyl ester, its iminothiol methyl ether, and a trimethyl derivative of the parent system; when the alkylation is performed with Me1 and methoxide, partial replacement of sulphur by oxygen may occur.99 The reaction of N-acetyltrichloroacetaldimine with the amides (156; R1 = R2 = alkoxy, X = 0 or S) proceeds more slowly when X = 0. The reaction between the aldimine and the acylated amides (157) proceed readily irrespective of whether X is oxygen or sulphur.loO Ring opening of the oxadiazaphospholes (158) by alkoxide
132
Organophosphorus Chemistry
yields the two hydrazides (159) and (160).101 1.3. Uses of PhosDhoric Acids and their Derivatives.-The cyclic phosphoramidochloridothioate (161) is effective as a phosphorylating agent when used to prepare mixed dialkyl phosphates through sequential reaction with alcohols in the presence of a tertiary amine.1°2 The cyclic chloride (162; X = 0, R = S02Me) likewise
phosphorylates with ring opening to give triesters, whereas the last stage of this process does not proceed with (162; X = S , R = Me).103 2-Deoxy-carbohydrate S-phosphorodithioate dialkyl esters act as glycosyl donors to partially protected sugars to give 2'-deoxydisa~charides.~~~
Compound (163) is useful in the cyclization of (?-aminoacids to p-lactams,1°5 and compound (164) is a reagent useful in peptide synthesis.lo6 Further examples of the use of cyanohydrin diethyl phosphates (here used in conjunction with SmI2) to give
nitriles have been recorded.lo7
2,Phos~honicand PhosDhinic Acids and their Derivatives 2.1. Svnthesis of PhosDhonic and P h o m'nic Acids and their Derivatives.- (a)phosr>honic Halides and related comDounds . The inevitable examples of C-phosphorylation of unsaturated systems (PC15 followed by SO2 or HCOOH) have appeared108 but more interesting
examples of this reaction sequence include the formation of the 1,4dihydro-1,4-azaphosphinine 4-oxide (165) from diacetamidelo9 and the diazaphosphinine (166) from N-acetyl-N'-methylurea.llo Perfluoroalkylphosphonic dichlorides have been prepared from the free acids in their reactions with 2,2,2-trichloro-2,2,2trihydro-l,3,2-dio~abenzophosphole.~~~ Several preparations of phosphonic acid monochlorides (as their mono esters) have been recorded: they were obtained from diesters by the action of PCl5, POC13, or (C0C1)2.112'116 Of particular interest here are those
compounds derived from isoprenoid phosphonic acids116 used (see later) to prepare analogous phosphinic acids, and the compound (167) used in the synthesis of inhibitors of cholesterol biosynthesis115. The mild conditions required when using the pyridinium salts with oxalyl chloride are worthy of note.117
5:
133
Quinquevalent Phosphorus Acids
S,
P
R’OH
,NMe
Et3N
0” ‘CI
-
S,
R20H
,NMe P
Melrn
0” ‘OR’
~
R1O,I
R20’
0
PSCH2CONHMe I
i, eq.NaOH ii, H3O +
/p R200 ‘\OH R’O,
H
o
x
A f
\
(168) X = I
OH
0 OSiPh2But : MeO, I I ,P+COOMe CI
t
A 2
\
OH
134
Organophosphorus Chemistry
The breakdown of S-trifluoromethyl phosphorothioates into phosphoryl fluorides has already been referred to; that of (S)-(-)-S-trifluoromethyl t-butylphenylphosphinothioate in pyridine at 0-20 yields racemic t-butylphenylphosphinic fluoride.4 The reaction between 1,1,2,3,3,3-hexafluoropropyl azide and diphenylphosphine oxide yields diphenylphosphinic fluoride.2 (b) Alkvl and Aralkvl Acids. Perfluoroalkylphosphonic acids have been prepared following the alkaline hydrolysis of difluorotris(perfluoroalkyl)phosphoranes, and they have been converted into their One-pot conversion of trimethylsilyl esters using E t ~ N S i M e 3 . lA~ ~
aralkyl chlorides into aralkylphosphonic acids (mostly already known) using the Arbuzov reaction has been reported.l18 The latter reaction still receives considerable attention, e.g. in the synthesis of intermediates leading to phosphonic acid derivatives of amino carboxylic acids I other interesting applications being the synthesis of the carbohydrate phosphonates (169; R = Me or Ph) from the iodide (168),120 and of esters of 3,5-di-t-butyl-4hydroxybenzylphosphonic acid (170); the latter are also obtainable from a trialkyl phosphite and the appropriate aralkyl alcohol.121 With N-bromosuccinimide, the ester (170; R = Et) yields the M-bromo derivative which can then be made to undergo a further Arbuzov reaction to give the gem-diphosphonic acid tetraethyl ester (171),122 also obtainable from triethyl phosphite, diethyl malonate, and 3,5-di-t-butyl-4-hydroxybenzaldehyde.l23 Treatment of the esters (171) with bromotrimethylsilane followed by hydrolysis yields the corresponding gem-diphosphonic acid (171; R = H) acidolysis of which results in the loss of both t-butyl groups.122 When the esters (170) are treated with Pb02,124 or (171) likewise with alkaline potassium ferricyanide,123 their conversion into the quinonoid acid esters (172) or (173) occurs. Base-catalyzed addition of dialkyl hydrogen phosphonate to (173) affords the trisphosphonic acid hexaalkyl esters (174).124 More details have now emerged of the reactions between trialkyl phosphites and benzothiete. The latter evidently acts through its o-quinonoid form (175). The products are the phosphonic esters (176), also obtainable from the sequential treatment of (175) with phosphorus trichloride and the alcohol ROH; the use of dimethyl phenylphosphonite leads to the phosphinic ester (177). By contrast,
5:
as
Quinquevalent Phosphorus Acids
P(OR)3
@s
-
-
[ w-&( 135
~
(175)
t
Ph-P-OMe
(177)
-Ph
(183)
(184)
(185)
Reagents: i, CI2P(O)CH2Y, Et3N, C6H6; ii, LDA, THF; iii, RX; iv, H 3 0 +
Scheme 18
136
Organophosphorus Chemistry
the cyclic phenylphosphonites (178; n = 2-5) yield 2:l adducts, consisting of 12- to 15-membered ring compounds (179). A reaction using (180) gives the dibenzo[d,h][l,6,2]oxathiaphosphepin 7-oxide (181) whilst cyclic pinacolyl phenylphosphonite yields (182). 125 Perkow reactions have provided phosphonic and phosphinic acid analogues of phosphoenol pyruvate (6; R1 = Me, R2 = OPr or NMe2; R1 = Ph, R2 = OEt or Ph).9
Scheme 18 outlines a procedure for the synthesis of chiral alkylphosphonic acids commencing with (R,R)-1,2-bis(methylamino)cyclohexane as the chiral auxiliary. The cyclic phosphonic diamide (183; Y = Me) is alkylated via the carbanion (LDA used as base) at temperatures lower than those employed previously and the products (184) obtained with even better selectivity. No racemization is observed during the acid hydrolysis step to the free acids (185). The formation of the major diastereoisomer (184), and hence of (185), is the result of attack by the lone electron pair in the more exposed position in the planar carbanion (186) on the alkylating reagent.126 The initial alkylation of the esters (R0)2P(O)CH22 (Z = CN, PhS02, MeS02, COOEt, or P(0)(OEt)2) with the dihalides Br(CHz),Br (n = 2 - 6 ) followed by cyclization, occurs under phase transfer conditions (K2CO3 in MeCN or DMSO), or in the presence of
NaH in THF/DMS0,127-130 (see also ref. 178) or, if Z = Ar, PhS, or MeS, in the presence of LDA/THF,lZ7 to give the cycloalkanephosphonic acid esters (187; R1 = OR); the reaction is also applicable to the cyclic phosphinic acid derivatives (187; R1 = Me).128t129 Another study employed the methylenebis(phosphonic acid) esters CH2[P(O)(OR)2]2 and the alkylating agents X(CH2)nX (X = Br or OTs, n = 3-5) in the presence of KH to give the esters (188) from which the free acids were obtained in the usual way. The acids (189), (190), and (191) were also obtained as esters. When n>5, substantial amounts of alkane- !?-,~-diphosphonic acids were produced.130 A one-pot synthesis of tetraethyl methylenediphosphonate has been described.131 Compounds of type (192; R1 = Me, X = H) have been obtained from dialkyl (iodomethy1)phosphonates by Arbuzov reactions130 or, for (192; R = H or alkyl, R1 = isoprenoid chain, X = H or F) by the alkylation of a phosphonochloridic ester with a lithiated dialkyl alkylphosphonate.l16 The action of an organolithium reagent on a trialkyl phosphate yields a lithiated dialkyl alkylphosphonate, but
5: Quinquevalent Phosphorus Acids
(189) X = C H (190) X = N
137
138
Organophosphorus Chemistry
the course and extent of this process depends on the particular lithium reagent and its method of preparation, and on the nature of the (thio)phosphoric acid substrate.132 The potential of the procedure for the synthesis of phosphonic diesters and diamides is discussed further in Section 2.l.i. Lithiated alkyl- and benzyl-phosphonic diesters have been treated with trialkyltin chlorides to give dialkyl [l-(triorganylstannyl)alkyl]phosphonates.133 The thermally-initiated rearrangement of ally1 phosphites e.g. (193), into allylphosphonates, here (194), is facilitated when R2 = COOMe; the products are then exclusively of the Z geometry. When R2 = CN, mixtures of E and Z products, the former in preponderance, are obtained.134 Reactions between phenylphosphonic acid or methylphosphonic acid and germanium(1V) dihalides have provided a variety of cyclic germanium esters of these acids. The compounds (195; R1 = R2 = Me, R3 = Ph) readily dimerize to the respective eight-membered ring compounds. The compounds (195; R3 = Me) are stable in solution, but readily decompose on attempted isolation even when R1 = R2 = mesityl.135 Other cyclic phosphonic esters and diamides have been reported.117 2,4-Dimethyl-1,3,2,4-dioxadiphosphetane 2,4-dioxide reacts with ethylene oxide to give 2-methyl-1,3,2-dioxaphospholane 2oxide.135 l-Phosphonoethane-2-sulphonic acid has been prepared from diethyl (2-bromoethy1)phosphonate and N a ~ S 0 3 . ~ ~ ~ Inosityl esters of short to medium chain length alkylphosphonic acid have been prepared through reaction between the phosphonic acid and the appropriate inositol penta-0-benzyl ether.137 Racemic 1,2:4,5-di-O-cyclohexylidene-myo-inositol is the source of the key intermediate (197; R = Bn) employed (Scheme 19) in the preparation of the methylphosphonic acid ester (200) and its phosphorylated derivatives (205) and (206) through a sequence of phosphorylation, esterification, and deprotection in the removal of benzyl groups by hydrogenolysis and of the propenyl group under mild acid conditions. The formation of (201) by the phosphorylation of (197; R = MeCH=CH) followed by mild acid hydrolysis, releases two
5:
Quinquevalent Phosphorus Acids
139
I Me
i, ii
“OCH=CHMe OBn (197)
OBn (198) R = Bn (201) R = CH=CHMe
YBnO’” R0Qif;OBn
f
0-P-OH I Me
iv
‘“OH
HO‘.
OBn
OH
(199) R = B n (202) R = H
1
(200)
v, vi
E1
0-P-OBn Me BnO’”
iv
w
”OP( OBn), OBn (203) R = B n (204) R = P(O)(OBn),
O H ;!- 0
ROQ HO”.
6
“OPO,H,
OH (205) R = H (206) R = PO3H2
Reagents: i, (196), dioxan; ii, BnOH, N-Melm; iii, 0.1 M HCI, CH2Cl2, MeOH; iv, H2, Pd/C, MeOH; v, (BnO),PNPrL, tetrazole, MeCN; vi, Bu’OOH
& R3w Scheme 19
R20’ R’,O; , , H
R4
7 ; S i
R‘
w
K2COdROH
Me3
R4
R3
I
OH (207)
140
Organophosphorus Chemistry
free hydroxyl groups thus allowing the preparation of the phosphorylated product (206) via (204), whilst if R = Bn, (205) is obtainable through (203).138 The synthesis of glycosylphosphonates and phosphonate analogues of myo-inositol tris(dihydrogen phosphate) has been reviewed.139 Dialkyl hydrogen phosphonates add to 1-aryl-2-nitroalkenes in the presence of a mild base to yield 3-(dialkoxyphosphinoyl)1-hydroxyindoles (207; R1 = OR2); the compounds (207; R1 = Ph) are obtained similarly.140 The addition of alkyl trimethylsilyl arylphosphonites to the same alkenes in a one-pot reaction yields the phosphinic acid esters (208) in good to excellent ~ i e 1 d s . lSome ~~ modifications to the preparation of dialkylphosphinic acids by the alkylation of phosphorus iodides and hydrolysis of the resultant polyiodophosphoranes takes into account the problem of water solubility of the products. 142 Bis(0-trimethylsilyl) phosphonite reacts with chloroacetic esters to give either the phosphonite (209), from which the corresponding phosphonate could presumably be obtained, or, the diester (210; R = Me) and hence, by hydrolysis, the phosphinic acid (210; R = H).l43 The optimum conditions for the reaction between 1,4-butanediyldimagnesium dibromide and an alkyl phosphorodichloridate have been investigated. The reaction leads to esters of the phospholanic acids (211; R1 = H). The comparable reaction between 2,5-hexanediyldimagnesium dibromide and ethyl phosphorodichloridate yielded a 1:2:1 mixture of diastereoisomeric 2,5-dimethylphospholanes, separable by liquid chromatography. Other ringsubstituted compounds were prepared by alkylation of ring lithiated compounds.144 (c): and ‘ c Acids. The interaction of trialkyl phosphites and various unsaturated halogen-containing compounds provides routes to alkenylphosphonic acid esters, although the course of the reaction may be influenced by the nature of the substituents at the double bond. Thus, the esters (212; R = Me or C1) yield the corresponding products (213) through a Perkow reaction, whereas (212; R = CN or P(O)(OEt)2 yield the esters (214).145 The related compounds (215) with triethyl phosphite-triethylamine yield mixtures of the
5: Quinquevalent Phosphorus Acids
141
0 HOP(CH,COOR), II
(Me3Si0)2PCH2COOMe
(210)
(209)
C12C=C.CH R(CO0Et) O=P(OEt), 1
CI,C.CH=CR.COOEt (212)
C13C.CH
poly(A)>>poly(G). formation with irradiation at 254 nm is consistent with a 2+2 cycloaddition with pyrimidine bases. The use of random screening as an efficient method to find DNA sequences that bind to proteins and other ligands has been reviewed.296 In the most general case a random mixture of oligonucleotides is incubated with the protein under investigation and the oligonucleotide-ligand complex separated from the mixture by an affinity technique. The polymerase chain reaction is then used to amplify the sequences that are bound to the ligand. Although this technique has most often been applied to the study of proteins, including the human transcription factor 297 and T4 DNA polymerase,298a similar procedure has been used to enrich RNA molecules from a random RNA pool that bind dyes resembling the redox-cofactor nicotinamide adenine dinucleotide.299 A review on the interaction of proteins with tRNA molecules, presented from a chemical perspective, has appeared.300
9. Interaction of Metals with Nucleic Acids.- The kinetics and mechanism of binding of cis-diamminedichloroplatinum(I1) (cis-DDP) and its inactive trans-isomer to DNA have been investigated by 195Pt nmr spectroscopy.301 Both isomers bind to DNA by 2 successive pseudo-first-order processes which initially form monofunctional adducts that subsequently close to produce bifunctional lesions. The monoadducts are bound predominantly at the N(7) position of guanine and retain a chloride ligand. Both
6: Nucleotides and Nucleic Acids
263
0 I -
H&OyBase
- Base
o+
P
/ \
-0
‘3
lo
0,
Scheme 13
HO
OH
H3h -‘3CH2CH2CH2’3CH2fNH2CH2CH2CH2CH:NH3
OH
0
(198)
(199)
264
OrganophosphorusChemistry
the cis- and trans-DDP monofunctional adducts react with glutathione to form sulphurcontaining species that cannot close to form the intrastrand DNA lesions. Preliminary experiments indicate that the trans-DDP monofunctional adducts react more rapidly then the corresponding cis-adducts suggesting that selective trapping of trans-DDP adducts in vivo could contribute to the biological inactivity of this isomer. The influence of glutathione on cis- and trans-DDP-induced alterations of DNA structure has also been investigated by polarography.302 The binding of cis-DDP to DNA induces a significant decrease in the melting temperature of platinated oligonucleotide duplexes. Whilst this effect can be attributed mainly to the kinked-cis-DDP-DNA structure destabilisation could also result from the reduced ability of the platinated guanine residues to base pair with cytosine. Oligonucleotide duplexes containing a base pair mismatch at the site complementary to the platination site have been investigated by thermal melting studies.303 The results demonstrate that cis-DDP coordination to N(7) of 2 adjacent guanines does not noticeably affect base pairing ability and therefore reestablishes the importance of the kinked structure. The effect on DNA of intrastrand cross-linking by a platinum anti-cancer drug has been studied by 13C-1H heteronuclear nmr using the model oligonucleotide d(TGGT) and cis-Pt(ethylenediamine)C12.304 The purine base 13C signals were characteristic of N(7) metallation whilst a large upfield shift of the C(3') signal in the first dG residue was attributed to an alteration of the sugar pucker. The same techniques have also been used to define metal binding sites in mononucleotides.~~~ 31P Nmr has been used to study the phosphato chelates formed when CTP and CDP are treated with cis-DDP.306 The major products result from platinum coordination through 2 adjacent phosphate groups of the nucleotides. Diplatinum complexes in which 2 nucleotide units bridge platinum centres through N(3) and terminal phosphate coordination in a head-to-tail fashion are the minor products. The efficiency with which Pt(I1) complexes cross-link phosphorothioate containing oligonucleotides to complementary DNA targets has been investigated.307 Cross-linking via a 5'-terminal phosphorothioate is more efficient than cross-linking through an internal phosphorothioate linkage and internal phosphorothioate linkages of the Sp-configuration cross-link more efficiently than those of the Rp-configuration. Several analogues of DDP have been prepared and evaluated as potential anti-tumour agents.3089309 It has been demonstrated that 6-coordinate ruthenium complexes containing bidentate aromatic diimine ligands are capable of enantiomerically selective interactions with double-stranded DNA.310 The basis of this enantioselectivity is believed to be the more favourable steric fit of the A (as opposed to the A) isomer within the minor groove of the DNA. Resolution of mixed-ligand diimine complexes of ruthenium has been performed by immobilising double-stranded DNA on a column of hydroxyapatite.311 Simple passage of the complexes through the column gives the A and A isomers in 95% or higher purity. 1H nmr studies on the interaction of the A and A isomers of [Ru(l,lO-
6: Nucleotides and Nucleic Acids
265
phenanthroline)3]2+ with the self-complementary oligonucleotide d(CGCGATCGCG)2 indicate that both enantiomers bind into the central AT-TA regions with a rapid exchange between bound and unbound states.312 The behaviour of the A enantiomer is essentially that of a minor groove binder with a preference for AT regions whilst the A enantiomer displays some major groove binding. Sequence-dependent structural modulations of the DNA helix have been studied using the A and A enantiomers of [Rh(1,1O-phenanthroline)2-9,lO-phenanthrenequinonediimide]3+ as shape-selective DNA binders that recognise and distinguish propeller twisted DNA sites on the basis of shape and symmetry.313 For example the propeller-twist of purines at the 5'-pyrimidinepurine-3' site is disposed in an orientation that permits facile intercalation of the Aenantiomer. The chiral discrimination demonstrates that the propeller twisting evident in crystal structures also occurs in solution and can serve as an important recognition determinant. The binding of Mg2+ to E. coli 5s ribosomal RNA has been investigated using 25Mg nmr spe~troscopy31~The results suggest that the binding sites fall into 2 categories: one in which Mg2+ is readily displaced by Na+ or K+ and a second that is less readily displaced by monovalent cations. More detailed studies of the coordination chemistry indicate that Mg2+-RNA interactions are dominated by hexahydrated ions held in the major groove.3 15 The interaction of the synthetic oligonucleotide d ( C G C G A A T T C G C G ) z with Zn2+ and Mn2+ has been studied by nmr spectroscopy.316 1H Nmr spectra recorded during titration of the transition metals showed distinct broadening effects on certain resonance lines. The results imply that the binding of both metals occurs in a sequence-specific manner which could be accounted for by local differences in the structure of the DNA and the basicities of potential binding sites, The rate of interaction between hydrogen peroxide and the DNA-Cu(1) complex has been shown to increase with pH and with increasing salt concentration, suggesting that H02- is involved.317 The interactions cause DNA damage due to the formation of -OH radicals near the site of Cu(1) fixation at DNA bases. The resultant DNA .OH species is able to reduce Cu(I1) to regenerate the DNA-Cu(1) complex and it thus appears as though a limited chain reaction is possible involving reductive propagation of DNA+OHspecies. 10. Analvtical and Phvsical Studies.- A variety of studies have appeared which have used new nmr techniques for the structural study of nucleic acids. Spectral congestion of the deoxyribose signals presents serious problems for nmr studies on oligodeoxyribonucleotides. A solution to this problem involves the suppression of nonessential proton resonances by regiospecific incorporation of deuterium. Deuterium incorporation at the l', 2, and 2" positions is particularly valuable because of the strategic involvement of these protons in the assignment process where by NOES are
266
Organophosphorus Chemistry
followed down a DNA strand from a base proton to the sugar to which the base is attached and on to the H(1') of the adjacent 5'-sugar. The methodology has been developed for the synthesis of thymidine, 2'-deoxyadenosine and 2'-deoxycytidine and 2'-deoxyguanosine containing deuterium at the l', 2' and 2" positions.318 The strategy involves the preparation of deuterated deoxyribose from ribolactone followed by nucleoside synthesis. A method for the simplification of NOESY spectra of DNA oligomers is presented that enables the selective tracing of the NOE connectivities of cytosine H(6) resonances by selective excitation of these protons via in-phase coherence-transfer from the cytosine H(5) protons.3 19 The dodecamer duplex d(CGCGAATTCGCG)2 containing a CG mismatch has been studied using 1H 3-D NOESY-total correlated nmr spectroscopy.3~The 3-D spectrum provides information for assigning all of the non-exchangeable protons including strongly over-lapping peaks in the crowded spectral regions such as those in the vicinity of the H(5') and H(5") protons. Conformational mobilities in the B- and Z-forms of d(CG)3 in solution have been compared in the microsecond and nanosecond time scales using the nmr techniques of on-resonance proton rotating-frame spin-latice relaxation and NOE respectively.321 The results indicate that the B-form d(CG)3 is more mobile than Zd(CG)3 on the nanosecond time scale although the converse is true on the microsecond time scale. The aggregation of GPD and GTP has been studied by nmr spectroscopy using Mn2+ induced paramagnetic relaxation.322 The data are consistent with the formation of stacked nucleotide dimers which can associate by hydrogen bonding at concentrations greater than 190 mM to give octameric units. The conformations of ADP, ATP and some ATP analogues have been studied by 2-D ROESY nmr experiments.323 Whilst the conformation of the adenine base around the glycosidic bond in ADP is very similar to that observed for AMP, with an equivalent population of the syn- and anti-conformations, ATP shows a preference for the high-anticonformation. 13C and 15N nmr spectroscopy have been used to investigate protonation of the homodimers d(CpC), d(TpT) and d(ApA) by trifluoroacetic acid in DMS0.324 The results show that for d(CpC) the capability of the 2 N(3) nitrogens to accept a proton is slightly different. In both d(TpT) and d(ApA) the protonation of the phosphate group leads to significant variations in the chemical shifts of the carbons adjacent to phosphorus. The conformation of DNA-bound spermidine has been studied by nmr spectroscopy using a 13C double-labelling technique.325 Spermidine was prepared containing two 13C atoms spaced 4 atoms apart (199). Long-range nmr coupling ( ~ J c c ) between the two labelled atoms respond to the dihedral relationship in a typical Karplus fashion and the results demonstrate that the central bond in the C4 unit of spermidine adopts an anti-conformation when bound to DNA. Structurally aberrant base pairs that
6: Nucleotides and Nucleic Acids
267
result from deamination of cytosine and adenine have been studied by nmr spectroscopy.326 The application of positive ion fast atom bombardment combined with collisionally-activated dissociationlmass-analysed ion kinetic energy spectroscopy (CADIMIKES) has been used to differentiate the 2'-, 3'- and 5'-monophosphate isomers of adenosine, guanosine and cytidine.327 Pentacoordinated oxyphosphoranes are intermediates/transition states for the hydrolysis of RNA. Whilst the properties of these pentacoordinated species are not easily elucidated experimentally a number of recent ab initio studies on the cyclic oxyphosphorane dianion have been carried out as models for the RNA cleaving process.328-330 The results of these and similar studies on an acyclic oxyphosphorane system 33 1 suggest that these dianionic species should exist as true intermediates although their stability is likely to depend on the nature of the axial substituents. The opening of a central base pair in a B-DNA oligomer has been simulated by Brownian dynamics using a previously developed model for DNA opening in which a base is allowed to rotate towards the major groove.332 Analysis of the rotation angle as a function of time enables the lifetime of the base pair and activation energy for the process to be estimated. This study indicates that the bases are continually subjected to rapidly fluctuating deviations from their equilibrium positions. Over longer periods the fluctuations add up statistically to produce states where the base pair hydrogen bonds are broken and the base protons are fully accessible to solvent. The first images of DNA have been obtained by photoelectron imaging.333 Since the image is formed by valence electrons emitted from the highest occupied orbitals the information obtained complements existing methods of imaging. Poly(9-vinyladenine) has been conjugated with agarose and its application to the electrophoretic separation of nucleic acids investigated.334 The conjugated agarose gel was able to discriminate between single- and double-stranded DNA and showed nucleobase-selective separation of RNA. In particular, the mobility of poly(U) was significantly retarded. As part of a model study to examine the effects of ionising radiation on DNA the products obtained from exposing a frozen aqueous solution of thymidine to y-radiation have been examined.335 Evidence has been obtained for an N(3)-centered radical formed by deprotonation at this position of the thymidine radical cation.
Organophosphorw Chemistry
268
1.
2. 3. 4. 51 6.
7. 8. 9. 10. 11.
12. 13.
14. 15.
16.
17.
18.
19. 20. 21.
22.
23.
24.
25. 26.
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Organophosphorus Chemistry
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7
Ylides and Related Compounds BY B. J. WALKER
1 Introduction Reports of theoretical and, especially, mechanistic studies are much reduced this year although phosphorus-stabilised carbanions continue to be very extensively used in synthesis. The range of heterocyclic systems synthesised by aza-Wittig reactions and related methods continues to increase as does the number and complexity of the phosphonates used i n natural product synthesis. A variety of new methods of introducing fluorinated-alkyl functions have been reported. 2 Methylenephosphoranes 2.1 Preparation and Structure.- Ylide formation from the reaction of carbenes and carbenoids with heteroatom loan pairs1 and the synthesis and chemistry of P-halogeno-substituted phosphorus ylides2 have been reviewed. Yet another ab iriitio M. 0. study of the structures, energies and electronic properties of the phosphorus and nitrogen ylides (1) has appeared.3 The results indicate that the phosphine imine structure (2) is c a 29 kcalmol-1 less stable than the isomeric aminophosphine (3). Variable temperature 13C n.m.r. studies of specifically deuterated alkylidenetriphenylphosphoranes (4) show that rotation about Ca-P, aryl-P, and Ca-CS bonds is tortionally unrestricted even at -1000 C . 4 I11 the case of the corresponding benzylidene ylides ( 5 ) both 1H and 13C n.m.r. spectra show temperature dependence. This is rationalised as restricted rotation (with a barrier of 8.5 kcalmol-1) about the C,-phenyl bond arising from resonance stabilisation of the carbanion by the phenyl substituent. Substituent effects on 15N, 31P, and 13C n.m.r. spectra of a range of N-phenyl-P,P,P-tri(4s u b s t i t u t e d p h e n y 1) - p h o s p h a - h 5 -azenes, triarylphosphines and triarylphosphine oxides have been reported.5 The ylide (8) has been generated, for use in a synthesis of the ichthyotoxin (+)-latrunculin A , by reaction of butadienyltriphenylphosphonium bromide (6) (generated in situ) with the dilithio dianion ( 7 ) (Scheme 1).6 The ylide-cation ( 1 0 ) has been prepared from 0 xylenebis(tripheny1phosphonium) ion (9) by reaction with phosphorus trichloride and triethylamine.7 Compound (10) reacts with methoxide and hydroxide to give (11) and (12), respectively, and can be protonated to give the symmetric dication (13) which, on the basis of 3 1 P - H c o u p l i n g 277
278
Organophosphorus Chemistry
+ -
+ -
H3X-Y H
H3P-NH
H,P-NH,
(3)
(2)
(l)X=Y =N X=Y=P X=N,Y=P X=P,Y=N
+
Ph3P-E{
R
H (4) R = H, Me, CMe3, or SiMe3 (5) R = Ph
P
+
h
3
P
w
Br
Ph,fp-
i
Br-
ph3 OLi Reagents: i, LDA, THF, -50
O O T M S
OLi (8)
"C;i i , & O w T M S (7)
Scheme 1
+ -AM I
Et3N
Ph,P=
o P P h 3
Ph3P
r
+
(9)
ol"
g +3LPh3 Ph3P
Ph3P
H
PPh,
p\
OMe
'H
7: Ylides and Related Compounds
279
measurements, is suggested to have a planar, tervalent phosphorus atom. 2 Oxocycloalkyltriphenylphosphonium ylides (14) have been prepared from triphenylphosphine by an electrochemical, one-pot synthesis of the corresponding salts followed by base treatment.8 Further investigations of the reactions of trialkyl phosphites with activated acetylenes have been reported and show, by trapping and 13C labelling studies, that such reactions involve the ketene ylides (15) as intermediates when carried out i n the presence of carbon dioxide.9 1,2hS-Azaphosphines (17) have been prepared from 1 - t - b u t y l - 1 , 2 - d i h y d r o - 1,2h3-azaphosphinines (16) by methylation on phosphorus, thermolysis of the resulting phosphonium salts and, finally, treatment with potassium carbonate.10 On exposure to air the h 5 azaphosphinines are oxidised to phosphine oxides (18). X-Ray diffraction has been used to determine the structure of a wide range of ylides. A dimeric structure, hydrogen bonded via carboxylic acid and keto groups, has been revealed for the keto acid ylide ( 1 9 ) by this technique.11 The structure of the thiole-containing ylide (21), formed by the reaction of the zwitterionic tri-ti-butylphosphine-carbon disulphide adduct (20) with two equivalents of dimethyl acetylenedicarboxylate, has been confirmed by X-ray crystallography. 12 X-ray determined structures have also been reported for the adduct (22)13, formed from the reaction of dimethyl acetylenedicarboxylate with acetylenebis[phosphonobis(dimethylamide)], the novel ylide (23),14 and the crystalline lithium compound (24) formed by treatment of the appropriate borane-ylide adduct with butyllithium. 15 Finally an X-ray structural analysis of the bismuthio-ylide ( 2 5 ) shows that the BiCylide bond length is 2.16A, only 0.05A shorter than the Bi-Cph single bond.16 2.2
Reactions
of
Methylenephosphoranes
2.2.1 Aldehydes.- P-Oxidobenzylidene ylides of phosphorus (26, X = P ) and arsenic (26, X=As) have been generated and allowed to react with aliphatic a l d e h y d e s . 1 7 In both cases styrene derivatives (27) were the only alkenes formed however, whereas i n the phosphorus case stereoselectivity was poor, in the arsenic case the reaction was (E)-stereospecific. 3-Hydroxypropyltriphenylphosphonium ylide ( 2 8 ) has been used as a 3-carbon synthon to construct the 6-membered ring in a new enantiocontrolled synthesis of indolizidine alkaloids (29) from prolinals.1 8 The highly substituted ylides (30) have been used in Wittig reactions to synthesise trans-alkene dipeptide isosteres.I9 The phosphonium salt ( 3 1 ) , which has been prepared from serine, is a nucleophilic alaninol, and hence alanine, synthon.20 Wittig reactions with (31) proceed with >93% retention of optical purity and, depending on the reaction conditions and the aldehyde used, high stereoselectivity to provide a new route to a,P-unsaturated amino
Organophosphorus Chemistry
280
R&pph3
(14) n = 1 , 2
(RIO),P
COP
+ R202CCECC02R2
+ (R'O)3PHC02R2 /
-
/
C
C02R2
d'
OR2
C02Et r-&o,Hph3p+0..
EtO2C
+
Bun3P-C:
s S-
*'?PPh3
o +, 0
28 1
7: Ylides and Related Compounds 3NaN(SiMe3)2
(Me3N)$CH2PC12 BPh4
-
,SiMe3 (Me3N),P=C,
P=N, (23)
SiMe,
BiPh, Me
(OH Ph2X +/
X=As, P
Br-
2BuLi
lm RCHO
Ph2Xf R
0-
1
282
Organophosphorus Chemistry
0 P~~P=$XO~BU X (30) X = CHzPh, C H ~ C O ~ B U ’
N H O ’
+
+
y01
1-
0PPh3
CH2PPh3
(31)
(32)
+ +
NaN(SiMe3)p
R1R2NH + Ph,P--CH&ECH Br-
R’R2N
R’ R2N
CH,
(33)
R3CH0
R3
+
Ph3P=CHC02Et
R2W +
R3
\
R4
/
C02Et
o +
*2R
R3
\ ~4
R2@
R3 CHCO2Et
H
‘ R4
CH2C02Et
7:
Ylides and Related Compounds
283
acids and alcohols.Trans-4-alkenyl oxazoles have been synthesised with >95 % stereoselectivity by Wittig reactions of the tri-a-butylphosphonium ylides ( 3 2 ) .2 1 These ylides were superior to the corresponding triphenylphosphonium ylides and to the phosphonate analogues. Treatment of the P enamino phosphonium salts ( 3 3 ) , available from the addition of amines to propargyltriphenylphosphonium salts, with base followed by addition of aldehydes provides a convenient synthesis of 2-amino- 1,3-butadienes i n generally good yields.22 Similar reactions with a,P-unsaturated aldehydes lead to cyclisation to give ( 3 4 ) . Aldehydes are converted to alkenes by palladium-catalysed reaction in the presence of tri-n-butylphosphine.23 The reaction gives moderate to good yields, is mostly highly stereoselective and takes place under neutral conditions.23 2.2.2 Ketones.- Methylenation of ketones can cause difficulties. A study comparing the use of the Wittig and Tebbe reagents in this reaction has appeared.24 Investigations of Wittig reactions with 1,4-naphthoquinones,2s 1 , 4 benzoquinones,26 and 1,2-benzoquinones27 have been reported. The reactions of 1,2-benzoquinones with ethoxycarbonylmethylenetriphenylphosphorane give a variety of products, e.g. ( 3 7 ) and ( 3 8 ) , in addition to the expected coumarin derivatives ( 3 6 ) .27 The initially formed 1,2-quinone methanide intermediate ( 3 5 ) can be trapped as a pyran derivative by carrying out the reaction in the presence of ethylvinyl ether. Wittig reactions of phosphacumulenes, e.g. ( 3 9 ) and ( 4 0 ) , have been i n v e s ti g a t e d .2 8 Sta bil i sed tri bu t y 1s t i boni um met h y 1ides ( 4 1) u nderg o olefination reactions with carbonyl compounds to give moderate to excellent yields of (E)-a,P-unsaturated acrylic acid derivatives.29 2.2.3 Ylides Coordinated to Metals.- The aza-rhenium (VII) ylide ( 4 2 ) has been reported.30 X-Ray crystallography shows that the rhenium atom in ( 4 2 ) is tetrahedrally coordinated to the four nitrogen atoms. The metal complex (44) is formed by the oxidative addition of methylenetriphenylphosphorane to the ruthenium carbonyl ( 4 3 ) .3 1 the structure of ( 4 4 ) has been determined by X-ray methods. Alkylidene transfer from a phosphonium ylide to tungsten has been used to prepare the complex ( 4 5 ) .32 Other examples of ylides coordinated to metals reported include complexes with rhodium (I) and rhodium (III)33 and the novel ylidicaluminium heterocycle (46).34 2.2.4 Miscellaneous Reactions.- a-Vinylidene-y-butyrolactones ( 4 8 ) have been prepared in excellent yield by Wittig reactions of the ylides ( 4 7 ) with gaseous ketene.35 The thermolysis of 2-diazo- 1,3-diketones ( 4 9 ) with 1,3-
284
Organophosphorus Chemistry
Ph,P=C
=C =X
Bu3~b-EHE
(39) x = 0 (40) X = S
NAr -NAr \ NAr
/
Ph,P=N-Re
(41) E = C02R, CN, or CONR2 (42) A r =
+
C,I
Al
Ph3P=CH2
M ,e O*pph3
Me2
? r12
ArC-CAr
(49)
CH2=C=O-
C4-h
+o R
R
A
+
? Tr
ArC-C=C=O
__.I
, xI
Ph3P-CH-C-R
(51) X = NPh (52) X = O (53) x = s
7: Ylides and Related Compounds
285
ambident-nucleophilic ylides ( 5 1 ) . ( 5 2 ) , and (53) leads to reaction either directly with ( 4 9 ) or with the ketene ( 5 0 ) formed from ( 4 9 ) by Wolff r e a r r a n g e m e n t . 3 6 The reaction provides routes to a variety of monoheteroatomic five- and six-membered rings. The reaction of ester-stabilised phosphonium ylides with cyclic anhydrides, known to give enol lactones ( 5 4 ) , has been the subject of a detailed study.37 1 -Amino-4-triphenylphosphoranylidene-5 -0xo2-pyrrolines ( 5 6 ) or a,P-unsaturated hydrazones ( 5 7 ) have been obtained in good yield by the reaction of conjugated azoalkenes with ethoxycarbonylmethylene ylides (55).38 The structure of one example of (57) was determined by X-ray crystallography. V i c i n a l tricarbonyl compounds (59) have been prepared in excellent yield by potassium peroxymonosulphate-induced cleavage of the ylide bond in substituted ylides ( 5 8 ) . 3 9 The ozonides (60), obtained from mono-substituted alkenes, are reported to react with stabilised ylides to give the corresponding alkenes in good to excellent yields.40 Monomeric selenobenzophenone ( 6 1 ) has been prepared in solution by the reaction of diphenylmethylenetriphenylphosphorane with selenium.41 A number of reports of routes to perfluoroalkenes have appeared. Perfluoroacylmethylenephosphoranes are insufficiently reactive to undergo the Wittig reaction, even with aldehydes. However treatment of the doublystabilised ylides ( 6 2 ) with alkyllithiums generates the ylide-anion ( 6 3 ) which, following protonation, collapses to give (64), mainly as the (E)-isomer, thus providing a novel synthesis of P-perfluoroalkylated a , P - u n s a t u r a t e d nitriles,42 ketones and esters43 (Scheme 2). Benzylidene ylides, generated i n situ, react with methyl 2-perfluoroalkylynoates ( 6 5 ) to give a mixture of adducts (66) and (67).44 This mixture, on heating in aqueous methanol, gives (Z)-methyl 3-perfluoroalkyl-4-substituted phenylbut-3-onates ( 6 8 ) with high stereoselectivity. A new, one-pot synthesis of fluorinated bromoallenes ( 7 0 ) is provided by the reaction of pentafluorophenylmethylenetriphenylphosphoranes (69) with bromoacetyl bromide (Scheme 3).45 The flash vacuum pyrolysis of sulphonyl-stabilised phosphonium ylides ( 7 1 ) has been investigated and shown to result in the loss of triphenylphosphine and sulphur dioxide to give alkenes ( 7 2 ) as the major products, possibly by a carbene mechanism.46 It is suggested that a new 0 to C rearrangement of allylphosphinic esters ( 7 3 ) to give ( 7 5 ) proceeds v i a an intramolecular mechanism involving an intermediate ylide ( 7 4 ) (Scheme 4).47 This C-C bond forming reaction has been applied to the synthesis of squalene. Reactions of the phosphonium aza-ylide anion (76) with electrophiles have been extended to provide a one-pot synthesis of various N-substituted phosphinines ( 7 7 ) .4* The reactions of N-vinylic-(78) and N-dienyl-(79) 15phosphazenes with various electrophiles have been investigated and shown to
Organophosphorus Chemistry
286
-o2c9-&:' 0
11
(54)
+PPh, R=H
H02c9?-(c02Et 0
=A-
Me
RICH
N=N -R2
+
cH/
PPh3
y
Ph3P= CHC02R3
THF or MeOH, -20 "C
Me R2NHN=,&-C=CHCO2R3 I
NNHR~
R1 Ph3P R$e
(56)
0 (57)
"'do) + 0-0
Ph,P=CHX
X = C02Me, COPh (60)
-
R
'
d
X
287
7: Ylides and Related Compounds Se Ph3P=CPh2
+
II
Se
-
Se
(61)
(63)
(62)
Reagents: i, RLi, THF, -60 "C; ii, CH3C02H, 0 "C; iii, 20 "C
Scheme 2
Ph,&H2Ar
B r + RfCECC02Me (65)
1
C02Me Ph, P =C' )=CHAr
K2CQ
Ar Ph3P=C' )=CHCO,CH,
+
Rf (66)
Rf
1
Me02C RfH
(67) MeOH, H20
y
r
(68)
Ph,P=CHR
i
- Ph,P=CRCeF,
ii
H,,c=c=c: Br
(69)
Scheme 3
Ph3pYAr' S02CH2Ar2
(711
c6F5
(70)
Reagents: i, C6Fs,THF, -20 "C; ii, BrCH2COBr, THF, -60 "C
Ar CH=C HAr2
R
Organophosphorus Chemistry
288
E
osi Prig
i, ii
Me2C=CHCH,yOCH2CH=CMe2
I
Me2C=CH CH=P-Ph I
OCH,CH=CH,
Ph
(74)
(73)
I
1
n
V
II OH
Me2C=CH-CH-P(
Ph
I
Me,C=CH CH,
.
0
II
Reagents: i, 2xLDA, THF, -78 OC; ii, Pf3SiOSCF3,THF, -78 "C
II
0 Scheme 4
Ph,P=NLi
RX
Ph3P=NR
flPPh2,
(77) R = 02S-@H3, -
(76)
Br, S03Et, or S02NEt2
N//PPh3 Et02CL
P
Ph
JJ ~
h
5
~
~
~
EtO2C
(78)
(79)
R1*H Ph3P+
Br-
(82)
I
Ph3P+ (83)
Reagents: i, CH2CI2,25 "C; ii, R'CHO; iii, R'CH=CHCHO Scheme 5
Br-
3
7:
Ylides and Related Compounds
289
provide routes to 2-aza-l,3-dienes, conjugated carbodiimides, Z-azahexa1,3,5-trienes, and pyridines.49 The phosphinimine ( 8 0 ) and prop-2ynyltriphenylphosphonium bromide react at room temperature to give the adduct ( 8 1 ) . Addition of aldehydes to (81) leads to the formation of p enaminophosphonium salts ( 8 2 ) or substituted tetrahydropyridines ( 8 3 ) depending on the nature of the aldehyde used (Scheme 5 ) . 5 0 The p enaminophosphonium salts ( 8 2 ) will undergo further reaction with aldehydes to provide routes to 2-vinyl- 1 -aza-1,3-dienes and penta- 1,4-dien3-ones. 3 The Structure and Reactions of Phosphonate Anions An X-ray structure determination of lithium diethyl benzylphosphonate carbanion has been carried out.51 the carbanion is crystallised in the presence of DABCO and the adduct formed has the structure ( 8 4 ) . The slightly pyramidalised configuration at the benzylidene carbon and the conformation around the C-P bond are reproduced by uD initio M. 0. calculations. N.m.r. (13C, 6Li, and 31P) and X-ray crystallographic analyses of the anion ( 8 5 ) of 1,3dimethyl-2-isopropyl- I ,3,2-diazaphosphorinane 2-oxide have been reported.52 The results show that the carbanion is almost planar and that the barrier to rotation about the P-C carbanion bond is very low. A new, more economical route to enantiomerically pure phosphonate ( 8 6 ) , which is a synthon for the preparation of mevinic acid, has been reported (Scheme 6 ) . 5 3 The method avoids the disadvantages of the competitive retro-aldol and @-elimination of the siloxy group observed i n an ear 1 i e r route . I sopr e no i d ( p h o sp h i n y 1met h y 1)p h 0 s p h o n ate s ( 87) have bee n synthesised by the reaction of methyl- or difluoromethyl-phosphonate carbanions with isoprenoid phosphonochloridates (Scheme 7).54 The electrochemical reduction of 1 -chloroalkylphosphonates ( 8 8 ) and ( 8 9 ) i n the presence of various electrophiles has been investigated.55 The initially formed carbanion is shown to undergo protonation, alkylation or olefination in the presence of acid, alkyl iodides or carbonyl compounds, respectively. Carbanions ( 9 0 ) , derived from cyclic phosphoramidate carboxylate esters, react with aldehydes in the presence of certain secondary amines to give (2)-alkenes highly stereoselectively.56 The new Wadsworth-Emmons reagents ( 9 l ) a n d ( 9 2 ) have been synthesised and shown to undergo olefination reactions with carbonyl compounds to give, ultimately, 2,4-pentadienals and 3-methyl-2,4-pentadienals, respectively, predominantly as the (2E,4E)-isomers.57 The reagent (91) has been used in the key step in a short synthesis of (E,E)-coriolic acid (93). Phosphonate-based olefinations involving (94) are reported to be superior to ylide or aldol methods in a new synthesis of 3-(polyen)oyltetramic acids ( 9 5 ) . 5 8 The olefination reaction of the aldehyde ( 9 6 ) with the bisphosphonate ( 9 7 ) under very specific conditions has been used to synthesise the isosteric bisphosphono analogue ( 9 8 ) of p - D -
Organophosphorus Chemistry
290
I DN/ M 5 PyMe +
OSiMe2But C02H
i,ii
I
C02Me 0 I1
Reagents: i, LiCH,P(OMe),
-
0
0
OSiMe2But
(MeO)2~&C02Me
(86) , THF, -78 O C ; ii, CH2N2, Et20 Scheme 6
I":
$?:
$?
(R10)2PCX2Li+ R2PCI
R2rCX2P(OR1)2 0
6R3
~
3
i, ii
? :
R2PCX2P-OI
0-
I
0-
(87)
X =HorF Reagents: i, TMSI, CH2CI2;ii, KOH Scheme 7
Me R1
(91) R = H (92) R = Me
29 1
Ylides and Related Compounds
7:
OH
MeA
(93)
yu{
1(0Et)2
II
BuO
(Et0)2PCHZCH2
!
OCOPh
+ [(EtO)2P12CH2
i, ii b
(96) Reagents: i, DBU, LICI, MeCN; ii, H2, Pt02
Scheme 8
0
+ PhS02CF$(OEt)2
f-:
PPW2 OCOPh
BuO (98)
(97)
R'R2C0
= 0-3
y
0
0
OH
Me
(95)IJ
(94)
RWC=C:
(99)
(100) z = 3-6
F
502ph
292
Organophosphorus Chemistry
fructose 2,6-bisphosphate (Scheme 8 ) . 5 9 A new, convenient, phosphonatebased r o u t e t o vinyl fluorides has been reported.60 The a f l u o r o m e t h y l p h o s p h o n a t e carbanion ( 9 9 ) was generated itz situ from fluoromethylphenylsulphone and allowed to react with ketones to give a fluoro-a,p-unsaturated sulphones. The phenylsulphonyl group is easily removed by reduction. A range of a,o-dithienyl polyenes ( 1 0 0 ) have been prepared by ylide-based or phosphonate-based olefination reactions with the appropriate bis-ylide or bis-carbanion.6 1 Phosphonate-based olefination continues to be used in the synthesis of tetrathiafulvenes and their derivatives. Three new vinylogous derivatives ( 1 0 1 ) of bis(ethy1enedithio)tetrathiafulvene have been prepared by such methods.62 A wide range of symmetrical and unsymmetrical 1,3-dithiole, e.g. ( 1 0 2 ) and ( 1 0 4 ) , and 1,3-selenothiole, e.g. ( 1 0 3 ) and ( 1 0 5 ) , derivatives have been synthesised by olefination reactions of the carbanions of phosphonates (106).63 Both symmetrical ( 1 0 7 ) and dissymmetrical ( 1 0 8 ) acetylene analogues of tetrathiafulvene have been prepared by the use of ylide-based and phosphonate-based methods.64 The report contains a discussion of the limitations of such methods. Some of the difficulties encountered can be overcome by using cobalt complexes, e.g. ( 1 0 9 ) , rather than the free acetylenic aldehyde in the olefination reactions.65 The base-induced reaction of P-substituted cyclohex-2-en-1 -ones with diethyl cyanomethylphosphonate ( 1 10) has been carried out and the effect of various reaction conditions on the stereochemistry of the olefin formed investigated.66 The reaction of 2,2-disubstituted 1,3-cyclohexadiones with dimethyl methylphosphonate anion provides a synthesis of 3-substituted 2cyclohexenones ( 1 1 1) rather than the expected olefin product.67 The yields are improved by the presence of trimethylchlorosilane i n the reaction mixture and a mechanism involving (a) initial addition of carbanion to the carbonyl group, (b) retroaldol cleavage, (c) proton exchange, and ( d ) intramolecular olefination is suggested. The reaction has been used in a new a-acoradiene ( 1 12). synthesis of (2)The alkylation of phospholanate ester carbanions ( 1 1 3 ) has been i n v e s t i g a t e d . 6 8 The stereochemistry of the reaction can be controlled to a large extent by varying the reaction conditions and by the choice of ester function. Alkylation reactions of the chiral, phosphorus-stabilised carbanions ( 1 1 4 ) are reported to be generally highly stereoselective and the stereoselec tivity is independent of the nature of solvent, additives and base.69 a - P h o s p h o n o - i o d o ( 1 1 5 ) and -seleno ( 1 1 6 ) lactones have been prepared from ethyl (diethoxyphosphory1)acetate anion by alkylation with allylic bromides and iodo- and seieno-lactonisation, respectively.7 0 Compounds ( 1 1 5 ) and ( 1 1 6 ) undergo olefination reactions with paraformaldehyde to provide a convenient synthesis of a - m e t h y l e n e - y -
7: Ylides and Related Compounds
(102) (103)
293
x=s
(106) X = S, Se
X = Se (104) X = S (105) X = S e
R’
OHC-CiC-CHO [CO~(CO)~I 4
R2
Is)=CH-C3-CH<sX R’
R2
0 II
(EtO),PCH,CN
(107) R 1 = R 2 (108) R’ + R2
R2
-
c“ R2
:
“OR’
R3X
Li + (113) RZ = H, CH2Ph
*
OR’
R3
R2
o
+
CP
“OR’
R3
But (114)
294
Organophosphorus Chemistry
*
0
x (115) X = I (116) X=SePh
0
k (117)
Reagents: i, R2C=CHCHzBr; ii, - OH; iii, NaHC03, 12,KI,or PhSeBr, THF; iv, DBU, Benzene: v, Na, (HCHO), , THF
Scheme 9
R O
Li 0 I
I1
RC-P(OEt)Z OSiMe,
i
.
I
II
R1COy-P(OEt)2 OSiMe,
(122)
Reagents: i, RICOCI; ii, H30+
Scheme 10
Ph,P=C,
,C02CHzPh OCH2Ph
ii +
R~COCOR
7: Ylides and Related Compounds
295
lactones (117) (Scheme 9) and the method has been applied to the synthesis of frullanolide (1 18). A range of a-fluoro P-keto esters, e.g. (121), have been prepared by acylation of fluorocarbethoxymethylenetri-n-butylphosphorane ( 1 19) and the carbanion of a -fluoroalkylphosphonate (120) followed by hydrolysis.7 1 The reaction with the phosphonate (120) could be extended to fluorinated acyl chlorides. A new route to 1,2-diketones is provided by the reaction of the phosphonate carbanion (122) with non-enolisable acyl chlorides followed by hydrolysis (Scheme lO).72
4 Selected Applications in Synthesis 4.1 Carbohydrates.- A Wittig reaction of [(benzyloxy)(benzyloxycarbonyl)methyl] triphenylphosphorane (123) with 4-0-benzyl-2,3 :5,6-di-O-isopropylidene-D-mannose has been used to synthesise 3-deoxy-D-m a 11 110- 2 octulosonic acid (124).73 A diastereoselective synthesis of P-C-ribofuranosyl glycines (1 25) by reaction of ribofuranoses with phosphoryl glycine ester carbanions has been reported.74 4.2 Carotenoids, Retenoids and Pheromones.- C h i r a l pheromone components (126) and (127) of A d o x o p h y e s species have been synthesised using Wittig reactions foIlowed by catalytic hydrogenation to construct the carbon chain.75 Standard Wittig methods have been used to synthesised (128) and (129), the main sex-pheromone components of Leucotera scirella and Perileucotera coffeella, respectively.76 Wadsworth-Emmons reactions of the 1,4-diacyl-( lE),(3E)-butadienes, obtained from rhodium-catalysed reactions of furans with ethyl diazoacetate, have been used to synthesise retinol-carotene fragments, (2) - 6 ( E ) - LTB 3 leukotrienes, and the dodecahexaenoic dicarboxylic acid, corticrocin.77 Standard Wittig methods have been used in the synthesis of photoactivatable analogues (130) of 1 I-cis-retinal.7 8 4.3 P - L a c t a m s . - A thiolester-phosphorane cyclisation strategy has been applied to the formation of the five-membered ring in the synthesis of olivanic acid analogues, e.g. (131)? One unexpected problem encountered was the partial isomerisation at C-3 in the P-lactam precursor used to form the intermediate phosphonium ylide. The carbon framework of the carbopenam ( 1 3 2 ) has been constructed using an intramolecular phosphonate-based olefination to form the five-membered ring.*() An alternative intramolecular Wittig route to penams involving the ylides ( 1 3 5 ) has been reported.81 The ylides ( 1 3 5 ) are prepared by the reaction of either stabilised or unstabilised ylides with the p - 1 a c t a m
Organophosphorus Chemistry
296
e.g. KOBU', CH2C12
(CH2)"OAc (128) -R (129) -R
(126) n = 9 (127) I/ = 1 1
= .---Me = -Me
I
C02p NB
-JSiMBL .. ...
g + R i
11, 111
0
C02R
(133) Y = CMe2 (134) Y = 0 X = 2-benzothiazolyl
C02R
(135)
Reagents: i, Ph3P=CHR1 ; ii, 03;iii, A, Benzene
Scheme 1 1
C02R
7: Ylides and Related Compounds
297
disulphide (133) (Scheme 11). The method was also applied directly to the keto analogue (134) of (133), thus precluding the ozonolysis step.
4.4 Leukotrienes, Prostaglandins and Related Compounds.- T h e c o n f o r m a t i o n a l l y - r e s t r i c t e d LTD4 analogues (136) and ( 1 3 7 ) have been synthesised using stereoselective Wittig olefination to give (Z)-(138) and (Z)( 1 3 9 ) , respectively, as the key step.82 The phosphonates ( 1 4 1 ) and ( 1 4 2 ) have been synthesised by acylation of the cupromethylphosphonate ( 1 4 0 ) and used in olefination reactions.83 The olefination method, involving simultaneous addition of the phosphonate( 1 4 1 ) and the appropriate aldehyde to a suspension of sodium hydride, has been applied successfully to a synthesis of the keto-12 leukotriene LTB3 ( 1 4 3 ) . Both phosphonium-based ( 1 4 4 ) and arsonium-based ( 1 4 5 ) ylides have been used to synthesise lipoxins A4 and B 4 . 8 4 Other examples of the use of Wittig olefination i n syntheses of this type include that of the acetylenic ylide ( 1 4 6 ) i n a new total synthesis of ( l l R , 1 2 S ) diHETE (147)85 and a concise synthesis of fatty acids, e.g. ( 1 4 9 ) , containing the (R)-hydroxy-(E,Z)-diene subunit.86 I n the latter case three equivalents of ylide are used to induce elimination i n the tosylate (148) and subsequent Wittig condensation. Wittig reactions of the phosphonium salt ( 1 5 0 ) have been used to synthesise the arachidonic acid analogues (151) and (152)87 arld consecutive Wittig reactions provide a route to the eight, rigid analogues (153) ( S c h e m e 12)P Phosphorus-based olefination methods continue to be widely used i n prostaglandin synthesis. Examples include that of the thromboxane receptor antagonists EP90289 and the calcium salt (154),90 the latter is orally active, and various analogues for use as F2a photoaffinity probes.91 4.5 Macrolides and Related Compounds.Phosphonate-based olefinations continue to be widely used in the synthesis of a wide range of macrocyclic compounds. An intramolecular olefination of the complex phosphonate (155) has been used as the cyclisation step in a synthesis of the aglycon methyl ester of the polene macrolide pimaricin.92 Other examples of the use of reactions of complex phosphonates include the construction of the carbon skeleton i n a synthesis of the twelve-membered macrolide m e t h y n o l i d e 9 3 and a total synthesis of FK506, a potent inhibitor of the expression of early T cell activation genes, involving the phosphonaniide carbanion (156).94 Model studies and theoretical methods have shown the feasibility of using a tethered phosphonate reagent of the appropriate chain length to establish the correct stereochemistry of the exocyclic unsaturated ester at C-13 in a synthesis of bryostatins.95 The method was then applied to the synthesis of ( 1 5 8 ) , a lactonised derivative of an advanced intermediate
298
Organophosphorus Chemistry
I"$:.... C13H27
do (1 36)
$?
(E~O)~PCH~CU
$?
RCOCI
(Et0)2PCH2COR (141) R = C R H ~ ~
(141)
+
OHC-
C02Et
1
OCOPh
NaH THF
.
7
1
H
s
C
C02Et OCOPh
(143)
299
7: Ylidrs and Related Compounds
OH
+
-
3Ph3Po
(CH2)3C02R
TsO
r
(148)
C02Me
+PPh,
q
I-
p
+
i,ii
I-
c
q
PPh3
\
-
f?ii,i"
R'
{ R 2
\
R'
R'
(153)
/=\ R' = n-C5HI1,H2C n-C,H,, R2 = (CH2),C02Me ,H2C/-7(
\
CH2),C02 Me
Reagents: i, Bu"Li; ii, R'CHO; iii, R2CHO; iv, LiOH, DME, H20
Scheme 12
Ca.2H20 2
300
Organophosphorus Chemistry
0
OTBS
(157)
\LiCI,
Lq EtsN, CH3CN
\
0
R
; OCH20R
C02Me
OTBS Ph3P+
Br-
Ph,P
OSiBu‘ Me2
7:
Ylides and Rrluted C'ompoirntls
30 1
in the synthesis of bryostatin, through the use of the phosphonate ( 1 5 7 ) . A Wittig reaction of the ylide derived from the complex phosphonium salt ( 1 5 9 ) has been used as the key step i n a total synthesis of milbemycin a1.96 An improved procedure, in which the ylide ( 1 6 0 ) is generated i n the presence of the aldehyde, has been applied to the synthesis of a number of milbemycin derivatives.97 Other examples of the use of Wittig reactions to construct complex carbon skeletons for the synthesis of macrocycles include a highly convergent synthesis of (+)-latrunculin A.98 T h e 26-membered macrocycle ( 1 6 l ) , containing two bipyridyl units, has been synthesised through the use of a quadruple Wittig reaction (Scheme 13).99
4.6 Nitrogen Heterocycles.- The application of the aza-Wittig reaction to the synthesis of heterocyclic compounds has been reviewed.100 Examples of heterocycles synthesised recently by this method include the isoindolol 1,2b ] [1,3,4]benzotriazepinone ( 1 6 2 ) , 4-quinolones (163),101 isoquinolines ( 1 6 4 ) , 1,9-diazaphenalenes (165),102 indolines and imidazoindoles,103 I H 1,2,4-benzotriazepines ( 166),104 SH-indeno( 1,2-h]pyridines (167),105 2Hindazoles (168) and the bicyclic derivative (169).106 The reactions of iminophosphoranes with heterocumulenes have also been widely used in heterocyclic synthesis. Hetero-condensed 2-alkoxy-4pyrimidinones, e.g. (171), have been prepared by the reaction of hetero- and carbo-cyclic 2-( triphenylphosphoranylidene)-3-~arboxylates, e.g. (170), with isocyanatesl07 and reactions of aromatic isocyanates with iminophosplioranes provide routes to pyrimido[4,5-d]pyrimidine derivatives (172).108 T a n d e m aza-Wittig/heterocumulene-mediated methods have been used to prepare lH-1,2,4-triazolo[2,3-b]indazoles(173)109 and fused [ 1,3,5]benzotriazepines (174) (Scheme 14).110 2-Methoxy-substituted pyrroles (175) have been prepared viu an azaWittig reaction by treatment of the appropriate azide with t r i p h e n y l p h o s p h i n e l l 1 and the aza-Wittig has been used to form the hydantin ring without epimerisation in a synthesis of (+)-hydantocidin (17 6 ) from fructose.112 The reaction of iminophosphoranes (177) with symmetrical dicarbonyl ( 178), dichlorides provides a route to N-substituted-phthalimides pyrrolidine-2,5-diones ( 1 7 9 ) , and piperidine-2,6-diones (180).113 2 - H Imidazoles (181) have been prepared by the reaction of N , N ' bi s ( t rip he n y 1p ho s p h oran y 1 i de ne ) bi s - ( be n zo tr i azol - 2 - y 1) me t h a ne d i am i n e w i t li aryl and alkyl Grignard reagents and subsequently with benzil.1 1 4 4.7 Miscellaneous Reactions.- The Wittig reaction of phthalaldehyde with the ylides ( 1 8 2 ) has been used to construct the carbon skeleton i n a new synthesis of dihydrocatalpalactone and catalpalactone (183, R=Me).I 15 A
Organophosphorus Chemistry
302
gCHO+ +
-
C h 3
i, ii
CHZPPh,
CHO
Reagents: i, LiOEt, EtOH, DMF; ii, H2/Pd/C
Scheme 13
303
7: Ylides and Related Compounds
~
0
NHN=C-N=PPh3 I
~
~
H 3
w
c
o -N
R2
COR'
R'
dr N-N
=PPh, H
2
~
3
Organophosphorus Chemistry
304
e
,
N
-N=PPh3
I \
I
NxR1
*
ii
@N=PPh3
iii
N"
N"
Reagents: i, Ph3P, CH2C12, 0 "C; ii, R'NCS, CH2C12, R.T.; iii, R2NCS, CH2C12, R.T.
Scheme 14
HocyL--p;
H
HO OH (176)
(175)
Ph3P=NR
X
NR
a
(177) R = Ph, CH2Ph,
(178) X =
CH2C02R, or QCH2
(179) X = (CH& (180) X = (CH2)3
N RXR N PhHPh
305
7: Ylides and Related Compounds
Qo
R
R
R' 02C
0
/C02Me Ph,P=CHOMe
KH
DMSO
Me
M e O o C H C 0 2 f v l e
,
.
&c
0
306
Organophosphorus Chemistry
short, total synthesis of (+)-norpatchoulenol ( 1 8 4 ) has been reported i n which a key step is the trapping of the unstable diketone intermediate ( 1 8 5 ) with methoxymethylenetriphenylphosphorane to provide ( 1 8 6 ) . 1 1 6 Both Wittig and phosphonate-based olefination has been used to prepare ( 18 7 ) and (188) which are readily converted into patulin ( 1 8 9 ) and neopatulin (190), thus providing a concise synthesis of the two latter compounds.117 An intramolecular olefination of the complex phosphonate ( 19 1 ) to generate (192) is a key step in a total synthesis of the aglycone of the novel cyclic diacetylenic antibiotic calicheamicin.118 The complex phosphonate ( 1 9 3 ) has been used as a late intermediate to construct the A-ring i n a synthesis of the ABC- ring system of brevetoxin B, a neurotoxin associated with the "red tide" phenomenon.119 The antibiotic, methylenomycin ( 1 9 4 ) has been prepared i n three-steps starting from diethyl 2-oxobutane(195) or diethyl 3-oxobutanephosphonate (196) o r phosphonate diphenyl(3-oxobuty1)phosphine oxide ( 1 9 7 ) . 1 2 0 In each case the c x o methylene function is introduced via an olefination reaction of the corresponding a-phosphorylcyclopentenone, e.g. (198). The carbanion of the chiral phosphonate ( 1 9 9 ) has been used as a key intermediate in a new synthesis of enantiomerically pure muscarine analogues.121 Both (+)-trans( 2 0 0 ) and (+)-cis-(201)-neocnidlides have been synthesised using an intramolecular olefination reaction of the phosphonates ( 2 0 2 ) and ( 2 0 3 ) . respectively, to form the 6-membered ring.122 The Wittig reaction has been used to generate "carba"peptide bond replacements, for example, i n the synthesis of the phenylalaninealanine analogue ( 2 0 4 ) . I 2 3 Alternatively, phosphonate-based methods can be used and these have been applied to the synthesis of the pseudodipeptides ( 2 0 5 ) and (206) (Scheme 15).124 REFERENCES A. Padwa and S. F. Hornbuckle, Chenz. REV., 1991, 91, 263. 1.
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307
LiBr
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HO
Et3N
Cgo
~
HO
\\\ Ill
\\\ 111
(191)
(192)
\-I
\-I
H
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H
H
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= ----H
=-H
CO2H
308
Organophosphorus Chemistry
Reagents: i, NaH, DME; ii, Hz,Pd/C; iii, Column Chromat.; iv, 6M HCI; v, Boc20
Scheme 15
309
7: YIides a n d Related C o m p o u n d s
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8
Phosphazenes
BY C.W. ALLEN
1 Introduction
This chapter covers the literature of phosph(V)azenes with reference to lower valent species when they can be related or transformed to the phosphorus(V) species. The high volume of activity balanced between basic and applied chemistry continues in this area. While there have not been any general reviews, the collected papers, including abstracts of posters, from the 11th International Conference of Phosphorus Chemistry (Tallin, 1989) have been published.' As in previous years, focused reviews will be cited in the appropriate sections below. 2
Acyclic Phosphaeenes
Interest continues in the area of acyclic phosphazenes, which are variously referred to as phosphazo derivatives, phosphine imines, or phosphoranimines. Reviews include a comprehensive and valuable survey of synthesis and reactivity of linear phosphazenes with emphasis on uses as synthetic intermediates in organic chemistry' , the use of N-vinyliminophosphoranes for the synthesis of nitrogen heterocycles ( in Japanese) , the synthesis of P-functional N-silylphosph~ranimes~, and the chemistry of iminophosphanes, phosph(III)azenes, including their conversion to phosph (V)azenes5. Ab initio MO calculations at a variety of levels of sophistication have been performed on monomeric and short chain phosphazenes. Calculations leading to estimation of heats of formation lead to the proposing of the experimentally unknown PNN-, NPN-, PNP-, and PPN- entities as new gas phase species.6 Two sets of calculations on H,PNH agree that the PN bond has high ylidic ~haracter.~'~ While H,PNH is calculated to be less stable than 313
Organophosphorus Chemistry
314
its tautomer, H,PNH,, the barrier to rearrangement is high.' The PN bond has multiple bond character but is dominated by coulombic interactions and shows little or no d orbital participation.' Conjugation effects have been explored at an LCAO-SCF level by investigation of the model compounds: (H,B) H,P-NH , (H,N) H,P=NH , H,P=NBH, and H3P=NNH2.9' lo The interaction of lone pairs which are coplanar with the formal double bond can strongly effect the stability and parameters of the geometric and electronic structures." The effect of inplane r1 bonding on the electronic transition energies of linear phosphazenes has been explored using semi-empirical CNDO/1 calculations. These (n') interactions lead to large optical transitions which can be modified by substituent electronegativity l1 Ab initio calculation on model short chain phosphazenes H3P(NPH,),NH (n=1-4) indicate the existence of PN bond length alteration.l2 Physical property measurements are dominated by NMR studies. The solid state 15N and 31PNMR spectra of [ 2,4 ,6-(Me$) ,C,H,N=P] +A1C14-have been obtained. The three components of the shift tensor have been resolved with the principle component being along the PN bond. The electronic environment is similar to other compounds with triple bonds to a nitrogen atom.13 The 15N, 31P and 13C NMR chemical shifts for a series of triarylphosphazenes, (pRC,H,),P=NPh, are controlled by the dipole of the RC,H, moiety which induces polarization of electron density within the PNPh unit. Correlations of the 'J,, data were examined using both the Hammett monosubstituent and the Taft dual substituent parameters.l4 A series of N=PPh, substituted pyrazoles, 1, provided a set of 13C shifts along with J13C3'P values. Coupling of the heterocyclic carbon atoms to phosphorus ('J, 3J, 4 J ) was observed.l5 The previously reported multiple NMR signals for Me,SiNPPh,CH,PPh, which were associated with restricted rotation about the PN bond have been shown instead to arise from chemical reactions of the molecule in question.l6 The dipole moments for a series of three coordinate phosph(V)azenes, R,P(=NR,)=NR,, have been obtained and used to calculate a PN bond polarity of 3.14D in the direction of phosphorus to nitrogen.l7 The use (MeZN),P=N-P ( NMe2)+, or P [ N=P ( NMe2)3] 4+ ions as phase transfer catalysts promotes 0-alkylation in the
.
8:
Phosphazenes
315
CI
Me
I
Ph
(7)
R’
2
CH2CH2CI
(9)
R
316
Organophosphorus Chemistry
reaction of dimethylsulfate with deoxybenzoin.“ The Staudinger reaction continues to be the most widely employed method of synthesis of acyclic phosphazenes. A few Staudinger reactions will be discussed in this paragraph, but most are the first step in a sequence where the phosphazene undergoes further synthetic transformation (see below). The C-2 symmetrical phospholane, (2R,5R)-l-phenyl-2,5dimethylphospholane has been used in the first enantioselective Staudinger reaction.‘ 9 The reaction of phenylazide with trans[PhNP(NMe,)], leads to the four membered ring with exocyclic phosphazene units (2,R=Ph; X=NMe,) A new synthesis of a valuable building block for metallocycle phosphazenes, Ph,P(=NSiMe,) NSiMe,, involves the reaction of Ph,PSiMe, with Me,SiN,. The Staudinger reaction of Me,SiN, with PhPR( CH2SiMe3) (R=Et, CH2CHMe2, Ph) gives PhPR ( CH2SiMe3)(=NSiMe,) .22 The phosphazotellurium derivative, Me,Te(N=PPh,), is obtained from the reaction of triphenylphosphine with the organotellurium diazide.,, The reaction of 3 (X=O, Y=N,) with triethylphosphite gives 3 [ X=O,Y=NP (OEt),] 24 A novel reaction of the coordinated o-benzoquine diimine 4 with triphenyl phosphine leads to 1,3,4RC,H, (NH,) N=PR, which is the major component of a tautomeric equilibrium with the cyclized h5-benzodiazaphosphole. The atrifluoro diazo compounds CF,CR=N, were characterized by derivatization with triphenylphosphine to the CF,CR=N-N=Ph, species.26 The reaction of ( [ 2- (diethylamino)methyl ] phenyl Jdiphenylphosphine with ethylcarbonazidate yields 1,2C6H4(CH,NRR’)PPh2=NC02R1’ which function as diuretics in rats.27 The use of carbon tetrachloride as an oxidant leads, via chloroform elimination, to dioxaphosphorinanes with exocyclic phosphoranimines. Thus, the reaction of 3 (X=lone pair, Y=NEt,) with CC1, and anilines gives 3 (X=NAr, Y=NEt,) and 3 (X=lone pair, Y=NHPh) with secondary amines and CC1, gives 3 (X=NRR’, Y=NPh) .24 Oxidative addition to phosph(II1) azenes represents another recently explored route to acyclic phosph(V)azenes. The reaction of RPClSiMe, with Et3CP=NCMe, gives the three membered heterocycle RkNCMe,P’CEt, via a phosphazene intermediate Me,CN=P (CEt,) =PR. The addition of RN3 to ClP=NAr gives a heterocyclic intermediate ClbN(R)N=NkAr which, in the case of large R groups, undergoes thermolysis to
.,’
.
‘*
8: Phosphazenes
317
a spectroscopically detected ClP(=NR)=NAr and on to the dimer 2 (X=Cl).29 In the case of the heterocyclic intermediate with R=CMe,, reactions with R’Li gives isolable R’P(=NAr)=NCMe,. 29 The attack of a-chlorolithium reagents, Cl(Li)C(SiMe,), on RP=NAr gives ArN=P(R)=C(SiMe,), presumable via a carbene route.,’ The reaction of RN=PPh, (R=l,2,4-trizenes) with diimides R’N=C=NR’ (R’=aliphatic) gives the Zwitterionic species (R’N)2E$(R)=PPh,.7 The oxidative addition of methanol to ( Me3Si),NN (SiMe,) P=NSiMe, gives (Me$ i) ,NN (SiMe,) PH (OMe)=NS iMe,.31 Sulfur or selenium oxidation of (Me2N),P=C (SiMe,) P=NSiMe, occurs at the phosph(II1)azenes center to form (Me2N),P=C (SiMe,) P=NSiMe, (X=S,se) 32 A one pot reaction of pRC,H,CN (R=CF,,Me,N) with LiN (SiMe,) 2, Ph,PCl and Me,SiN, gives a mixture of RC6H4C[N (SiMe,),] [ =NPPh,=N (SiMe,) ] and RC,H,C [ =N (SiMe,) 3 [ N (SiMe,) PPh,=N (SiMe,) 3 .33 A complex reaction is followed in the conversion of (EtO),PN(SiMe,)R to (EtO),P (=NR)C (CF,) ( OSiMe,) R’ by reaction with CF3COR’ A cyclic addition product 6C (CF,) ,C (CF,) ,Oh (OEt)=NCMe3 was also observed.34 The same silylaminophosphite when allowed to react with Me,CNO gives (EtO),P (=NR)N (CMe,) OSiMe,.35 The first triply bridging phosphazo coordination geometry is obtained in the photolysis of trans-NiC1(N3)(PMe3)2 which yields 5 or 6 depending on the wavelength employed. A direct synthesis of 6 from the Ni(I1) starting material and LiNPMe, was also established.,, Phosphorus(V) starting materials have also been used for synthesis of acyclic phosphazenes. The reaction of perfluoronitriles, RCN (R=C,F,, C,F,,, C,F,,) , with Ph,P=CR,’COR’’ provides cis and trans Ph,P=NCR=CR’COR” .37 The interactions of N-acetyltrichloroacetaldimine with [Ph2P(S)],NH leads to Ph,P ( S ) N=P (Ph),SCH (CC1,)NHCO,CH,. 38 The potassium salt of the C,H,CH,NP(X) (OCHMe,), (X=O,S) anion combines with Me1 in Me,CO to give C6H5CH2N=P(XMe)(OCHMe,) 39 Treatment of MeNHCONHC0,Me with PC1, gives [ C1,P=NCC1=CHPC1,]+PC1,-40 The reaction of (EtO),P(O)SiMe, with Me,CN=N(O) CMe, gave a mixture of products including Me,CN=P(OEt),OSiMe, which can also be obtained (along with other products) from (EtO),P (0) C1 and LiN ( SiMe,) CMe,. 41 The widely used I1PPN+I1ion can be easily obtained (in the form of (Ph,P),N+Cl-) from the reaction of Ph,P, PU1, and NH20H*HC1.42 Interest in reactions of the phosphazene unit, especially
.
.
,.
318
Organophosphorus Chemistry
in the synthesis of nitrogen heterocycles, continues to increase. The general strategy in these transformations is to generate a phosphoranimine, by the Staudinger reaction unless otherwise noted, which is allowed to react with a carbonyl moeity thus generating a reactive imine or carbodiimide. The reactive center is often adjacent to a substrate which can effect an intramolecular ring closure. This process is illustrated in the conversion of 7 to 8 by addition of RNCO to 7.43 The particular focus of this chapter does not allow for exploration of the elegant complexity of all of these syntheses so only the bare outline, focusing on the phosphoranimine will be mentioned for each citation. The most common carbonyl derivatives are the isocyanates which, as described above, provide carbodiimides. Heterocyclic and carbocyclic 2(triphenylphosphoranylidenamino)-3-carboxylates react with isocyanates to give 2-alkoxy-4-pyramidinones.44 The addition of ArNCO to PH,P=NCRC(O)R' followed by oxyalic acid gives amino-1,3-oxazoles.45 The interaction of aromatic isocyanates with 5-[N-arylimino]methyl-6[(triphenylphosphoranylidene)amino]-lI3-d~methyluracils gives functionalized pyramidino pyrimidines.46 Reduction of the imine gives materials which also undergo the same reactions to the hexahydropyrimido derivatives.46 In a complex series of annulations , the diazide 1,2-C6H4(N3)CH=N-2-C6H,N, upon reaction with triphenylphosphine and RNCO sequentially gives pentacyclic Enamino esters with 1,3 diamino [ 1,3 ,51benzotriazepines .47 units react with Ph,PCl, to a monoiminophosphorane which can cyclize with PhNCO to give pyrano[ 2 ,3-d]pyrimidine~.~* Pyrrolo[l,2-a]quinoxal~nesIindo[3,2-c]quinolines and indolo[l,2-c]quinazolines are available from aryl phosphoranimes with o-pyrrole or indole moieties upon reaction with isocyanates, CO, or CS2.49 The reaction of pyrimidine iminophosphoranes with isocyanates gives pyrido[2,3d]pyrimidine. Ring closure of P-aryl vinyl phosphoranimines via reaction with isocyanates leads to isoquinoline derivatives. Benzofuranones having attached p-iminoarenes are obtained from the reaction of the p-phosphoranimine with aldehydes.52 Phosphoranimines have been used in intramolecular aza-Wittig reactions to prepare pyrrolo-[1,2-a]benzimidazoles,
''
8:
319
Phosphazenes
fused quinazolinones, quinoles and an isoindolo[ 1,3 ,4 ] benzotriazepinone 53 The aza-Wittig reaction of l-(triphenylphoranylidene)-3-phenyl-2-th~oxo-4imidazolidinone with heterocumulenes gives fused imidazoles while with isothiocyanates forms imidazo[l,5d] [ 1,3 ,4 3 thiadiazines 54 Iminophosphosphoranes a to the nitrogen center in lr4-dihydropyridinesundergo addition and aza-Wittig annulation with acetylenedicarboxylates to give pyrido [ 1,2-a]pyrimidines.44 The phosphazide 2-Ph,P=NNC6H,CH=NPh cyclizes to 2,3-diamino-2H-indazole with a triphenylphosphoranylidene group in the 2-position which in turn add acyl chlorides and undergo acid catalyzed cyclization to fused indazoles.55 Anilinobenzoylpyrazoles with the anilino nitrogen atom converted to a C(0)CH2N=PPh, amide cyclize to benzodiazepinones.56 The intramolecular aza-Wittig reactions of hydrazones such as 2 ,4-Me02C(Br)C,H,NHN=C (C0,Et)N=PPh3 to give benzotriazepines is highly dependent on substituents.57 The reaction of tributy1(cyc1ohepta-1,3,5-trieny1imino)phosphoranes with a-P-unsaturated ketones gives 9H-~yclohepta[6]pyridinesvia a Michael-type carbon-carbon bond formation and subsequent azaWittig reaction.58 N-Vinyliminophosphoranes have proven to be valuable synthetic intermediates. The reaction of N-(1phenylviny1imino)triphenylphosphorane with 3 , 8 methano[ll]annulenone followed by dehydrogenation gives the 14a 1-aza-4I 9-methanocyclopentacyclo-undecene system.59 The interaction of tributyl(inden-3-y1imino)phosphorane with a,P The unsaturated ketones leads to 5H-indeno-(1,2-6)pyridines reactivity towards electrophiles of the N-vinyl iminophosphorane, EtO,CC(=CHPh)N=PPh,, has been examined. The aza-Wittig reaction with aldehydes and isocyanates gives the expected imines and carbodiimides. Treatment with acid anhydrides gives N-protected aminoacrylic acid derivatives. The reactions of PhCH=CHCH=C(CO,Et)N=PRPh, with PhCHO gives the imine when R=Me but with R=Ph cyclization to the diphenylpyridine-carboxylate occurs.61 Wittig precursors are obtained when the reaction Ph,P=NPh is allowed to react with propyl-2-ynyl-triphenylphosphonium bromide. The follow-up reaction with aromatic aldehydes gives P-enaminophosphonium salts, i.e., RCH=CHC(NHPh)=CHPPhiBr-. If a , p unsaturated
.
.
.,'
320
Organophosphorus Chemistry
aldehydes are used, tetrahydropyridines are obtained.62 Nphosphinyl-1-azaallyl anions add a, p unsaturated ketones to give phenylpyridines through an intramolecular aza-Wittig process.63 The addition of tri-n-butyl (or cyclohexyl) phosphine to ethyl-2-diazo-halonicotinoylacetates provides piperidinopyridazine carboxylates.& Arene imine derivatives of chrysene and benzo[g]chrysene can be prepared by the intramolecular reaction of vicinal alcohol and phosphoranimine functions.65 Addition reactions of phosphoranimines to give quaternary species are known. Addition of alkylhalides to Ph,PNR (NRlR”) gives quaternary ammonium compounds which on hydrolysis gives 2‘ amines& or amino acids.,’ Addition of acid chlorides to PhNHC (0) C (N=PPh,) =NNHC,H,X (X=H, Me , NO, , C1) leads to a quaternized nitrogen center which upon treatment with triethylamine give 1,2 ,4-triazoles The reaction of H2C( PPh2=NSiMe3) with Ph3GeC1 gives [Me,SiN=PPh,CH,P=N (SiMe,) GePh,]+Cl- which when treated with wet acetonitrile gives NH,PPh,=N=PPh,Me*Cl-. Direct treatment of Me,SiN=PPh,CH,PPh, with Ph3MC1 (M=Ge,Sn) in wet acetonitrile gives Ph,P(0)CH,PPh,.69 The addition of acid chlorides to Nvinyl phosphanimines gives the quaternized nitrogen species which add phenol to give azadienes or undergo hydrolysis to aamino acids. 70 The reaction of benzenediazonium The tetrafluoroborate with Ph,P=NPh gives [ Ph,PNPh,]+BF,‘. analogous quaternization occurs in the polystyrene derivative, [ CH2CH(C,H,PPh,=NPh) 3 which is prepared by radical addition polymerization of CH,=CHC,H,PPh,=NPh. 71 Hydrolysis chemistry is important in that one can consider the phosphoranimine as a protected amine. Thus hydrolysis of PhNHC(O)C(N=PPh,)=NNHC,H,X Vicinal diamines can be gives PhNHC (0) C (NH2)=NNHC,H,X. obtained from RCHBrCHR’NHP(0)(OH) by a sequence of conversion to the azide, Staudinger reaction with P (OEt) and hydrolysis.72 A preparation of the antibacterial moiety cefaclor goes through hydrolysis of the triphenylphosphino function in the last step to provide the primary amine site.n Pyridines with a C(O)C(=NN=PPh,)CO,Et entity in the 3 position can be hydrolyzed to the corresponding hydrazones.64 Alcoholysis reactions proceed in a manner analogous to hydrolysis reactions. The use of Ph2P(=NSO,C,H,CH,) 0 as a protecting group in benzoyl-protected
.,
,
321
8: Phosphazenes
glycopranose and its conversion to an RO unit upon reactions with alcohols has been developed.74*75 The reaction of Cl,P=NCH (CH,OH) CH (OH)C,H,NO, with methanol gives NHCH (CH,OH)CH (OH)C,H,N02 which along with related (MeO),P (0) species were prepared as bactericides, virucides, insecticides, ovicides and fungicides.76 A few miscellaneous phosphoranimine reactions serve to finish this section. The aziridino derivatives, (Et,N) (C,H,N) ,-,P=NR, react with the spirophosphoranes Cl,POC,H,O and C1,PN (Ph)N=C (CF,) 0 at both the phosphazene and aziridine units to provide four membered rings such as 9.77 The BF, catalyzed imide-amide rearrangement of (CX,O) ,P=NPh to (CX,O) ,P (0) N (CX,) Ph (X=H,D) has been examined. Both bimolecular and intramolecular pathways were observed.78 The reaction of Fe,(p-CH,) (CO) and RN=PPh, (R=ferrocene) gives a phosphorus free metallocycle (10).79 The other major class of reactions of acyclic phosphorazenes under consideration are those in which the phosphorus-nitrogen double bond stays intact during the transformation. The 4-phenylphenoxy derivatives, (RO),P ( 0)P (OR)3, ( RO),P ( 0)NP ( OR),NP ( OR) and (RO),PNP (OR),NP (OR),NP (OR),+PCl,- have been prepared from the chloro precursors and the aryloxide." The mercapto derivatives (RS),P=NP(O) C1, (R=Et, Pr, octyl) are available from Cl,P=NP(O)Cl, and the mercaptan in the presence of pyridine. An intermediate species, (RS),ClP=NP(O)Cl, was shown by ,'P NMR, to be in the reaction mixture.8' Bromination of RN=PCl,NR,' and Me,CN=PCl, with Me,SiBr provides RN=PBr2NR2' and Me,CN=PBr3.82 The lithio salt Ph,P=NLi can be converted to Ph,P=NR (R=C(0) R8,, C0,R8, , P (0)Ph?, S02C,H,Me67 , S0,C167) by reaction with the corresponding chloride and Ph,P=NBr by reaction with Br2.67 Reactions of Ph3PNS0,C1 with alcohols and amines give the appropriate sulfuryl derivative.67 The fluoroaryl derivatives Ph,P (=NC,F,Z) CHzPPh2 are obtained from the reactions of Ph2P(=NMMe3)CH,PPh, (M=Si,Ge) with F5C6Z (Z=N, CCN) .& The elimination of trimethylsilyl derivatives from the trimethylsilylphosphoranimines is widely used as a route to new phosphoranimine derivatives. The ReO, derivatives, ( O3ReN=PPh2) $HZ , ( 03ReN=PPh2) ,C2H4 and Ph,P=NRe03 are obtained from the trimethylsilyl precursors and Re207.85 The reaction of
,
322
Organophosphorus Chemistry
,
CF,=C ( CF,) with R,P=NSiMe, (R-OMe, OEt , We,) provides R,P=NCF=C (CF,) 86 Thermal decomposition of (EtO),P=NCF=C (CF,) The F, and CF,=C (CF,) CN. leads to ( EtO),P (0)F , (EtO)P (0) reactions of PhPF, with the trimethylsilyl precursors gives [ (Me,N),-,Me,P=NP(NMe,) ,-,Me,=N],P(Ph) F+PhPF,-(n=O,1) while { Ph,P [ N=P (NMe,) Me]2)+Ph,PF,- is obtained from Ph,PF3 and the appropriate trimethylsilyl derivative.87 Similar reactions with PCl, give ( Et,N) ,P=NPCl, , [ (Et,N) ,P=N] ,PC1 and [ (Me,N) Me,P=NP (NMe,) ,-,Me,=NPCl, 3. 87 The RNbC1, (R=$-C,Me, ; v5-C,Me,Et) reactions with trimethylsily precursors gives The reaction of Ph,P=NNbCl,R and [ RNbCl,N=PPh,] ,C,H,. Me,SiN=PPh,N=S (0) Me, with SeOC1, gives SeC1,[ N=PPh,N=S (0) Me2] .89 Derivatives of substituents on the nitrogen center in phosphoranimines also may be prepared. The reaction of 2,6diisopropylphenylisocyanate with Ph,P=NReO, gives Ph,P=NRe (NC,H,R,) 9* Silyl group exchange occurs when PhPR(CH,SiMe,) =NSiMe, is treated with Me2SiC1, to yield PhPR (CH,SiMe,) =NSiMe,Cl. 22 Phosphoranimines can function as Lewis bases in coordination compounds. The first reported borane adducts Ph3P=NR*BH3(R=Me,Et, n-Pr, i-Pr, i-Bu, t-Bu, Me,N, PhNH) can be prepared directly from BH3-THF or by reaction of the hydrobromides with LiBH,. Bis adducts, (Ph,P=NR) ,BH+I-, are obtained from the reaction of Ph3P=NR-BH21 with Ph,P=NR. The relative base strengths of the phosphoranimines have been established by BH3 exchange with other amine~.~’The reaction of [Rh$C1I2 where L=CO, cyclooctadiene (COD), with R3P=NR leads to 27 new Rh%Cl*NR=PR, complexes. The equilibrium between reactants and product depends not only on phosphoranimine substituents but also on L.92 The reactions of (CF3),PN=PPh3 with PdC1, and 0 s CO),,CH,CN and O s , (CO) (CF,),PN=Ph, lead to Pd,C1, [ (CF,) PN=PPh,] respectively. In each case, coordination is via the P(II1) center and both PN distance are equal indicating a delocalized PNP unit. Other examples of acyclic phosphazene reactions can be found in section 5. In addition to the cases noted above such as the diuretic other applications activity of 1,2-C,H, ( CH2NRR’)(Ph,P=NCO,R”) of acyclic phosphazenes have been suggested. Pyrimido[lI6,a]benzimidazoles with Ph3P=N substituents have been tested for
,.
,
,.
295
,’
6,
8: Phosphazenes
323
bactericidal and fungicidal activity.95 Phosphazocarbacyl esters, RC (0) N=PX, , have been examined for use as biocides .96 Plant growth inhibition is exhibited by Me2C=CHBuP(=NH)(OEt) 97 Rhizoxin esters with phosphono or alkylphospho substituents on the ester show antitumour activity toward mouse leukemia P388 .98 Nitro-fluorenimines with N=PR, groups on the imine nitrogen are used as electron acceptors in electrophotographic photoreceptors 99
,.
.
3 Cyclophosphazenes
The factors controlling the regio-and stereochemical pathways followed in the substitution reactions of halocyclophosphazenes have been reviewed in detail. Predictive schemes for the reaction pathways have been proposed.loo The influence of side groups on the ability of cyclophosphazenes to undergo polymerization or ring expansion has been reviewed.lo' A brief review in Japanese on inorganic phosphazenes is also available.Io2 Ab initio SCF-MO calculations on the (NPO), series have been performed. The cyclophosphazene dimer, 11, is a global minimum and the corresponding trimer is also predicted to be stable. Vibrational frequencies for these experimentally unknown species have been calculated.lo3 The nitrogen and phosphorus XPS data for (NPR,), (R=C1, F, MeO, CF,CH,O, C6H50) confirm the high polarizability of the PN bond induced by the exocyclic substituent. These results are interpreted using ab initio MO calculations.lo4 The phosphorescence spectra oi' hexakis(P-naphthoxy1)cyclotriphosphazene in both solution and rigid matrixes have been obtained and closely resemble those of naphthalene chromophore.lo5 The motion of guest molecules in cyclophosphazene inclusion compounds has been investigated using the narrow spinning side bands observed in the 'H MAS NMR spectra.lo6 The mass spectra of [NP(OPh)2]3,4 show 65 to 90% of the total ion current is carried by the M+ and [M-60]+ ions.lo7 Mass spectrometry has also been used to investigate the thermal degradation of [NP(OPh)2],,4. Above 4 4 0 ' the trimer gives a resinous solid plus volatiles include triphenylphosphate, phenylamine and phenylaminophosphates. The tetramer exhibits similar behavior at a lower onset temperature. The
Organophosphorus Chemistry
324
N
L o
O=P'
N''
8: Phosphazenes
325
decomposition of the partially substituted materials N3P3(OPh),.C1, starts at 280’ and gives the same products along with HC1.1°8 The kinetics of the reaction of N3P3C16 with CF,CH,OH under phase transfer conditions have been followed using gas chromatography. Second order rate constants for all six steps of substitution have been obtained. Interestingly, the rate of reaction for N3P3C1,0CH,CF3 is faster than N,P3C1, otherwise the expected decrease with increased degree of substitution is observed. These data indicate the operation of both electronic and steric effects.’09‘’10The rate of amidation o-nitroaniline by acetic acid in the presence of N3P3C1, and pyridine is independent of acetic acid and pyridine by linear phosphazene. The formation of N3P3C1,0C(0) CH3 followed by reaction with acetic acid to give N,P3C1,0H and acetic anhydride as the active agent was proposed.”’ The UV and NMR spectra of 12, its 1,2 naphthoxy isomer, and derivatives with the bis phenylamino and phenylenediamino moieties in place of the aryloxy groups suggest intramolecular interactions between the aryl R systems and the aziridine lone pairs. Strong intermolecular hydrogen bonding in the phenylamino and phenylenediamino derivatives was observed. It has been proposed that these interactions are related to the relative degree of cytostatic activity in these derivatives.’12 The cytostatic activity of aziridinocyclophosphazenes has also been suggested to be related to the conformation of the aziridino groups as reflected in their solid state structures.‘13 Cyclophosphazenes containing amino groups have been employed as curing agents and extensive testing of resulting resins has been reported.’14-’16 Bisphenol A type and novolak expoxy resins cured with N3P3(OPh) (NH,) , N3P3(OC,H,NH,) , N3P3( OPh) (OC6H4NH,) and N3P3(NMe,)3C13 have been subjected to viscoelasticity, tensile, thermogravimetry and chemical resistance testing.’I4 Expikote 828 expoxy resin cured with 2 ,2-N3P3(OCH,CF,) (NHZ) was superior to resins cured with N3P3(OPh) (NH2) or N3P3(NMe,) 3C13 as shown in modulus of rigidity, tensile strength, and chemical resistance testing. Similar studies show 2 ,2N,P3(OC,H,C1),(NH,), superior to 2,2-N3P3(OPh),(NH2), as a curing agent. l6 The only cyclophosphazene synthesis from non-cyclic
,
,
,
’
326
Organophosphorus Chemistry
precursors this year involves the photolysis of R,P(S)C=N-NPR, (R=i-Pr) which undergoes elimination of R,P(S)CN to give (R,PN) presumably via the monomeric phosphazyne.'17 Mixed substituent isothiocyanato derivatives N3P3R5NCS (R=OPh, OCH,CF, , OCH,CH,OCH,CH,OCH,) and N3P3(NMe,) (NCS) were mathematically prepared from the chloro precursor and KNCS.118 The reaction of the (NPC1,)3,, mixture with liquid ammmonia has been studied.'19 The diaryloxy derivative 12, its 1,2 naphthoxy isomer, the 2,2bis anilino and phenylenediamino derivatives are obtained from the reaction of aziridine with the appropriate chloro precursors.112 The remaining amine derivatives are all obtained from di or polyamines. The reaction of hydrazine and (NH,NH),P(O) OPh with N3P,C1, give the spirocyclic derivatives 13 (R=P3N3C1,, P(0) OPh) .120 The para substituted diamino linked phosphazene oligomers N3P3C1,[ NHRNHN,P,Cl,] "C1 [ n=1-5 : R=p-C,H, , p-C,H,C,H,, 1,11'-binaphthyl-4,4l-diylr p-C,H,EC6H, (M=O, S, SO,, CH,, CMe, N=N)] are available from N,P3C1, as are the analogous oxyo (0 in place of NH) derivatives.12' The reactions of oxodiamines continue to supply a plethora of interesting new structures. The reaction of NH, (CH,)3O (CH,),O (CH,),NH, with N,P3C1, in a two phase (Et,O/Na,CO, water) system gives the trans "dibinol'derivative ( N,P,Cl, [ NH (CH,),O (CH,),OCH,) ,NH] ) (14 n=2) .122 The products of the reaction of N,P3C1, with NH, (CH,) 3O (CH,),O (CH,),NH, are remarkably sensitive to reaction conditions.123 In a stirred homogeneous or heterogeneous THF solution the bridged species N3P3C15NH(CH,) 3O (CH,),O (CH,) ,NHN,P,Cl, is obtained.123'124 The spiro derivative N3P,C1, [ NH (CH,)3O (CH,)0(CH,),NH] is obtained as a by-product of this reaction.123 If an unstirred heterogeneous, THF/Na,CO, aqueous, medium is employed the reaction proceeds stereospecifically to trans 1 4 (n=6) 123*125 The reaction of N,P,Cl, with spermidine gives two products , 15 and 16, involving bridged tetramer units. The corresponding spermine reaction leads a single product, 17, which also has two bridged tetramer units. The NMR parameters for these new materials are compared to those for the analogous derivatives of N,P,Cl,. 126 The reactions of cyclophosphazenes with oxyanions continues to be the most widely explored of phosphazene reactions. This is in large part due to using the reactions at
,,
,
.
8: Phosphazenes
327
the trimer level to model reactions of poly(dich1orophosphazene). The simplest oxyanion, the hydroxide anion, has a complex pattern of reactivity which has again attracted attention. A detailed 31PNMR study of the hydrolysis of N,P3C1, in THF has been reported.'27*"8 The initially formed N3P3C1,0H or its tautomer (NPC1,),NHP(O) OH, reacts with additional hydroxide by both geminal and nongeminal pathways both eventually leading to the geminal , and NPCl, (NHP( 0 )OH) species. Oxobridged dimers ( N,P3C1,0H) O (N,P,Cl,) 2O have also been proposed"8 but the assignment of the latter has been shown to be incorrect from the NMR of an authentic (crystallographically established) sample.129 This sample was obtained from a reaction of N,P,Cl, with the monosodium salt of uracil in the presence of Bu,NBr which in addition to the substitution product 18 showed two hydrolysis products, the aforementioned dimer and N,P3C1,0-.129 The synthesis of N3P3C16-n(OR), (R=CF3,CH,109 , Phl3O) via phase trans catalysis (NaOH, Bu,NBr) has been shown to be a very efficient procedure. Significant rate accelerations have been observed and both mass transfer and chemical kinetics influence the rates of reaction. Column chromatography proved to be effective in separation of the trifluoroethoxy derivatives.lo9 Optimum conditions for the preparation of N,P, (OPh) (OC,H,NO,) have been patented."' The synthesis of the potential polymer precursors, 2 ,4-N3P3( OPh) (OR) (R=C,H,-p-CHO , C,H,-p-OH , CH,C=CH) , has been described.132 The treatment of 2 ,2N,P,Cl, (N=PCl,) with NaOR (R=Ph, CH,CF,) proceeds with sequential substitution initially at the exocyclic positions to provide 2,2-N3P,C1,[N=P(OR),], followed by formation of 2,2N3P3(OR) [ N=P (OR)3 ] 133 Numerous oxyanion derivatives with one substituent containing a reactive center suitable for further transformation have been prepared. These include N3P,C1,0 (CH,) ,OC ( 0 )C (CH,) =CH,l3, , N,P, (OR)5O ( CH2CH,0)3C,H4CH=CHC,H,N0,'35 , N,P, (OPh),O (CH,O)O , (CH,) ,NHOC ( 0 )OCMe313, and N3P3X,0C,H,CH0 , (X=C1, OCH2CH3).13' Fully substituted derivatives have also been ,CH,CH=CH, explored. The reaction HO ( CH2CH,0)7 M e and HO ( CH2CH20) with N3P,C1, was carried out to prepare precursors to polyelectrolytes Cyclophosphazenes with biphenyl mesogenic
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,.
.
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328
Organophosphorus Chemistry
groups have been prepared by reactions of the appropriate oxyanion with N3P3Cl,. Monotropic nematic texture in the range of 59-102 was observed for N3P3[ 0(CH2CH20) ,C,H,C,H,CN] but none of the related species, N3P3[ 0( CH2CH20),C,H,C,H,OR] 6 (R=Me, Et I Pr , iPr, Bu), were liquid ~rystalline.’~~ A nematic phase was detected for N,P, (OC6H,C,H,CN) by DSC and polarized microscopy but the related N,P, (OC,H,N=NPh) showed no mesomorphic activity.140 Both the trimeric and tetrameric 4-phenylphenoxy derivatives,
,
,
[ NP ( OC,H,C6H4) 2 ] 3 , 4 , have been prepared and examined by x-ray crystallography Treatment of a mixture of cyclic oligomersI (NPCl,),, with KOC,H,Br gives cyclic materials with bromophenoxy substituents.14’ Polyfunctional oxyanions have also been investigated as nucleophiles towards cyclochlorophosphazenes. The spiro derivatives, N,P,Cl,~,,R, (n=l,2 : R=2 ,2l-dioxy-1,1’biphenyl are available in two phase reactions from the alcohols and in turn treatment of the disubstituted material with sodium phenoxide or aziridine gives N,P, (R’) (R) (R’=OPh, NC2H4) 142 The reactions of N,P,Cl, with 2,2-dimethylpropane-1,3-diol results in the formation of a wide range of products reminiscent of the behavior of other alkane diols. The mono, di and tri spiro derivatives N,P3C1,-,,[ OCH2CMe2CH20], (n=l,2 ,3) , the 2 ,4 bridged (ansa) species, 2 ,4-N3P3C1,( OCH2CMe2CH20) I the mono spiro , mono ansa species, 18, and the doubly bridged species analogous to 14 with OCH2CMe2CH20in place of the oxodiamines have been dete~ted.’,~A similar array of products is obtained in the reactions of N3P,C1, with bis(2-hydroxyethy1)ether. The three spiro derivatives, N3P3C16-,,, [ (OCH,CH,) ,0], (n=1-3) I the ansa , i.e. , 2 ,4-N3P,C1,[ (OCH,CH,) 20] the spiro-ansa derivative analogous to 18 , the bridged species N3P3C1,0(CH,),O (CH2),0N,P3C1, and the doubly bridged entity analogous to 14 have been observed. An 0x0 bridged dimeric hydrolysis product N,P3C1, [ 0(CH,)2O (CH,),OH]ON3P,C1, was also obtained.144 The reactions of another diol, diethyl bis(hydroxymethyl)malonate, with N,P4C18 results in the formation of a series of spirocyclic materials which include N,P,C16[ (OCH,),C (C0,Et),] , 2 ,2 I 4,4N,P,Cl,[ (OCH,)2c (CO2Et)2 1 2‘ 2 I 2 I 6 ,6-N,P,C1, [ (OCH,)2c (CO,Et)212 and The product distribution and NMR N,P4 [ (OCH,)2C( C02Et)2]4. spectra were compared to those obtained in the propane-lI3-diol and the 2 ,2-dimethyl propane-1 ,3-diol series.145 The
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329
tetrafunctional pentaerythritol has been shown to undergo extensive reactions with both (NPCl,),,&. Products include the spiro bridged dimers 19 (n=l,2), the trimeric spiro ansa bridged dimer 2 0 and a mono spiro derivative with two free diol functions, N,P,Cl, [ OCH,C (CH,OH) ,CH,O] 146 The chemistry of heavier congers in the oxygen group is limited but interesting. The 1,l'-dichalcogenato ferrocene anions undergo reaction with N,P,Cl, to provide the spirocyclic derivatives N3P3C16(EC,H,) ,Fe],, (n=1,2,3i E=S,Se) of which 21 is an e~arnple."~ A limited number of new reports of the syntheses of phosphazenes with phosphorus-carbon bonds have appeared. The reaction of N,P3C1, with RMgCl in the presence of (n-Bu),PCuI followed by addition of Me3SiCH21 leads to 2,2'-N3P3C1,( CH2SiMe3)R (R=Et, CHMe,, Bu, CMe,, CH2CMe3,Ph) . Displacement of the remaining chlorine atoms by the trifluoroethoxide ion occurs clearly in toluene but some carbon-silicon bond cleavage occurs when THF is the solvent.148 The reaction of N,P,F, with LiCH,SiMe, provides N,P, (CH,SiMe,) in nearly quantitative yield. The geminal di- and tetrasubstituted species have been detected in solution.149 The appropriate Grignard reaction leads to N3P,C1, [ C,H, ( CMe,) ,] which undergoes ortho group activation upon treatment with aluminum chloride to yield 2 2 . 150 The sequential reaction of N3P3C1, with RMgX/ (Bu3P),CuI followed by aldehydes or ketones provides a general synthesis of the series 2,2'N,P,Cl,(R)C(OH)R'R" (R=Me, i-Pr, t-Bu; R'=H, Me: R"=Me, Et, CO,Et, CH=CHMe, C,H,FeC,H,, Ph, etc) . If R1+R1',the two =PC1, centers become non-equivalent and coupling may be observed in the ,'P NMR spectrum. Evidence has been obtained for coordination of the copper ion to the phosphorus center in the phosphazenocuprate intermediate.15' The reactions at exocyclic positions of cyclophosphazenes continues to play an important role in the chemistry of these materials. Some of these processes have been mentioned above. Fluoride ion induced carbon-silicon bond cleavage allows for conversion of N3P,(CH,SiMe,) to N,P,Me, in good yield. Treatment of 2,2-N,P3F4(CH,SiMe,) with NaOCH,CF, also leads to carbonsilicon cleavage to generate 2 ,2-N3P3(OCH2CF3) ,Me,. 149 The thermal rearrangement of N,P, (OR)6-n ( OC6H,Me) (R=Me, n=1-3 ; R=Et , CH,Ph, n=3) yields [ (NR)P(0) (OC6H4Me)1, with retention of the
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Organophosphorus Chemistry
330
Ph ,E=N, N II R2K
R3 I
R’
XNYPT)
rlR2
N N=E’ Ph
F;’? R2
(23)
R3
(24)
R
I
(25)
8: Phosphazenes
33 1
geometrical disposition of the aryloxy group. The mono and dimethoxy derivatives, N,P,(OMe)n(OC,H,Me),~, (n=1,2), provide Thiourethane and [ (NR)P (0) ( OC6H4Me)3 ,[ NP (OC,H,Me) ,] 152 thiourea derivatives are available from the reactions of alcohols and amines with isothiocyanato cyclophosphazenes.'la Thus the reaction of N,P, (NCS) with ROH provides N,P, [ NHC (S)OR], (R=Me, Et, Pr, Bu, Me,CH). The reaction follows a non-geminal pathway as shown by ,'P NMR detection of intermediates. Under similar conditions the mixed derivatives, N,P,(OR),NCS (R=Ph, CH,CF,, CH,CH,OCH,CH,OCH,) were unreactive. At higher temperatures the trifluoroethoxy derivative gives the expected reaction while 2,4,6-N3P,(NMe,)3(NCS)3 gives N,P3(NMe2)3(0Et)3 through a labile N,P,(NMe,),[NHC(S)OEt]3 intermediate. Reactions of N,P,(NCS), with amines lead to N,P,[NHC(S)NHR], (R=H, Me, Ph, Bu, C,H17) The tetramer, N,P,(NCS)a, undergoes similar reactions but with lower reactivity.'la Careful hydrolysis of N,P,Cl,-,(HNCN) , (n=2,4 ) gives the trimetaphosphimates, Na,[ (NH),P,O,-,(NCN) "1 .153 Radical addition polymerization of the olefin in N3P3C150(CH,),OC (0) C ( CH,) =CH2 gives a carbon chain polymer with the cyclophosphazene as a substituent. Copolymerization with methylmethacrylate has also been investigated. Reactivity ration data and the derived AlfreyPrice parameters show the phosphazene exerts a significant effect on the olefin rea~tivity.'~~ The sequential reaction of N,P, ( OCH2CF3)50C6H,CH0 with borohydride and methacryloyl chloride gives another organofunctional monomer, N3P,(OCH,CF,) ,OC,H,CH,OC (0) C (CH,) =CH,, which also undergoes radical addition polymerization at the olefinic center. Interestingly higher molecular weights are obtained at low conversion than at high conversion.13' Sidewise coupling reactions allow for synthesis of primary amino groups as side chains. The deprotection of N,P, (OPh),O (CH,),O (CH,),NHOC (0) OCMe, with trifluoroacetic acid gives a amine at the end of the CH,CH,C (0) substituent. Coupling with CMe30C(0)ONHCH,CO,hC (0) gives a 0(CH,) ,O (CH,)NHCOCH,NHOC (0) OCMe, side chain and the process may be repeated to give tripeptide substituents.'36 A cyclomatrix shift base phosphazene polymer is obtained from the The treatment of N3P3(OC,H,CHO) with p-phenylenediamine.15' synthesis of tetraphenylporphrine with N,P,(OPh)O units in the
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OrganophosphorusChemistry
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meta position of the phenyl groups is accomplished by the interaction of N,P3 (OPh),OC,H,-m-CHO with pyrrole. The Zn2* and Cu2* pyrophrin complexes are obtained from reaction of the neutral ligand with M(OAc), (M=Zn, Cu). The metal uptake rate is 100 fold slower than that for tetraphenylporphyrin.lS5 Metal complexes of a spiro oxodiamino derivative, N,P3C1, [ NH ( CH,) 3O ( CH,) ,O (CH,),NH] have been reported. Reaction with butyl lithium leads to the lithium complex of the monodeprotonated ligand which in turn adds MEt, (M=Zn, Mg) to give N,P,Cl, [ N (CH,),O (CH,) ,O (CH,),N] OM. All three complexes are dimers in the solid state with the Mg2+ complex involving one endocyclic nitrogen atom in the coordination sphere. The ionic conductivity of complexes obtained from the reaction of LiClO, [ OCH, ( CHZOCHZ) .CH20CH3] ) (n=l 2 ) is with ( CH2CHC6H4C6H40P3N3 comparable to that of the oligo(oxyethy1ene) derivatives of the poly (phosphazenes) lS7 Other cyclic oxyethylene derivatives such as N,P,R, [ R=O (CH,CH,O) ,C,H,-p-C,H,,] are excellent ligands for alkali metal salts and function as effective phase-transfer catalysts.'51 Preliminary reports of metal carbonyl activation of N3P3F5C=CPhhave appeared. Excess phosphazene in the presence of Co, (CO) gives the cyclotrimer 1 3 4-C, (N3P3Fs) ,Ph, which exhibits restricted rotation about the carbon-phosphorus bonds. The reaction with q5-C,H,Co (CO) gives a Co coordination cyclodimer, carbonyl insertion products and the cyclotrimer. similar reactions with Fe2(CO), are even more complex providing in addition to the species described above, a metallocycle and a novel product arising from an alkyne bridging iron and the oxygen of a coordinated cyclobutadienone.lS9 The formation of q6Cr(CO) coordination to phenyl groups on cyclophosphazenes has been examined in detail. The direction reaction of N,P,X,R with Cr (CO) gives N,P,X,R*Cr (CO) (X=F, R=Ph ; X=OCH,CF, R=Ph , OPh; X=C1 R=OPh; X=NH,C,H,, R=OPh) Alternatively N,P,Cl, and NaOPh. Cr (CO) gives N3P3C150Ph-Cr (CO) and N3P3X,R*Cr(CO) (X=F, R=Ph; X=C1, R=OPh) with NaOCH,CF, gives the trifluoroethoxy derivatives. Partial substitution can be accomplished as shown by the reaction of N,P,R, with Cr(CO), to give N,P,R,R*Cr(CO), (R=Ph, OPh, OC,H,Me, OCH,CH,OPh, NHPh) . Full loading of the metal carbonyl fragment can also be obtained as shown by the formation of N3P3[OR Cr (CO),] from N,P3C1, and NaOR Cr ( CO)3 . 160 I
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I
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Phosphazenes
333
While not an exocyclic group reaction, it is of interest to note the formation of sulfur trioxide complexes of N,P,(OPh),. Coordination is believed to occur at the endocyclic nitrogen atoms leading to N,P,(OPh),.nSO, (n=1-3). Different coordination arrangements in the tris adduct give rise to an A2B ,‘P NMR spectrum.’6’ The continued high level of commercial interest in cyclophosphazenes is demonstrated by the numerous patents filed citing applications of these materials. The extraordinary level of interest shown in derivatives of hydroxyethylmethacrylate , HO (CH,),OC (0) C (Me)=CH, (HEMA), noted last year continues unabated. Cyclomatrix materials from thermal or photochemical curing HEMA/cyclophosphazene derivatives exhibit good hardness, dimensional stability, mechanical strength, and chemical resistance.162 Improved properties are obtained by combining the HEMA derivatives with polymeric (or polymer precursors) materials. This approach has been used with fibers (glass ~ 1 0 t hpolyester’&) ’~~~ , to provide surface coated materials, acrylic resins’65, polyester containers’66, polyester film167,polyester sheets for ink ribbons in magnetic recording, etc. 168’169, in combination with siloxanes or reactive silanes to give water repellency and other low surface adhesion properties ( C,F12CH2CH,SiMeC1,’70, NH, ( CH,) ,S iMeOSiMe,171 , hydroxy1 terminated dimethy1s i1oxanes’72 ) and styrene based resin composites.ln Other HEMA applications include components of transparent laminated films in electronic devices’74, as antioxidants in powdered iron magnetic coatings’75 and in x-ray blocking materials.176 Mixed amido/alkoxy, aryloxy, alkylamino on dialkyl amino induce shrink resistance Amidophosphazenes provide wash and stain into cotton.17’ resistance in cellulosic fabrics.178 Other cyclophosphazene applications include antiradiation cover layers for electronic component^'^^, cross linking of expoxy resins114-116’180, aminophenoxyphosphazenes as flame retardants in polystrene blends’” , flame proofing of lignin and lignosulfonates with , heat resistant rnaterialsla3, chlorophosphazenes’s2 amidophosphazenes as catalysts for the condensation reaction of aminoplasts’% , and fluoroalkoxy derivatives as superior lubricants for metals.185
334
Organophosphorus Chemistry
There is a surprising absence of publications in this year. It remains to be seen if this reflects a trend or an aberration. 7 The aromaticity index calculated for Ph,P=NC(Ph)=NS(Cl)=h is in the range of the symmetrical triazines suggesting similar electron distributions. The reaction of R,P(NSiMe,) [N(SiMe,) ] with PhECl represents a good method for phospha(thia)zene synthesis. The reaction products R,P,N,E,Ph, (R=Me, Ph ; E=S , Se) exhibit the eight-membered ring structure 23. Hydrolysis of the S(V1) derivatives ~(NH,),NP(NH,),NS(O) (0M)k (M=Na+,Rb’, NH;) is reported to give the aminotrihydroxy species, h (OH),NP (OH)(NH,)NS (0)(OM)N’. 188 5 Miscellaneous PhosDhazene Containina Rina Svstems Includina MetallaDhosDhazenes
A review of the synthesis and reactivity of six and eight membered metallacyclophosphazenes1a9as well as a comprehensive review (in Russian) of the preparation, properties, structure, and reactions of five and six membered mono- and dicycl~phazenes’~~ are available. Aromaticity indices for F,hNCCCF,)NC(CF,)h are similar to the symmetrical triazenes while the values for phosphazene containing phospholes are low suggesting less aromaticity in the latter.‘& Addition of the cyclophosph(II1)azene ;=NC(Ph)=Nk(Ph) with amines and diamines and iodine or enamines give five membered monophosphazenes such as ( Et2N),b=NC (Ph)=Nh (Ph) and 2 4 . 19’ Hydrolysis of the spiro derivatives 2 4 leads to phosphorus-nitrogen cleavage in the spiro ring whereas in 2 5 the cleavage occurs at the phosphazene bond. In all cases the P=N center is the strongest base site.192 The reactions of azaphospholes, R,b=NCPh,C (C0,R)=E (C0,R) with activated arylazocarbonitriles give the 1,5,2-h5-diazaphosphorines 26 and 2 7 . 193 Six membered rings with one phosphazene , (Me,N),P=CHP (NMe,),=NC (R)=kH, are obtained in the reactions of (Me,N),b=CHP(NMe,)=CH with RCN (R=furan, pyrrolidine) .‘91 Deprotonation of the cyclic ammonium precursors gives Ph (Me);=NCH=CRCH=;R (R=Me, Et , Pr , Bu) 195 The reaction of acetylurea with PC1, provides 1
.
335
8: Phosphazenes
(C~~P=NCC~=NCC~=CH + PPCC~~~which ~ )upon treatment with SO, yields Cl,$=NCCl=NCCl=&H. 196 The addition of MeO,CC=CCO,Me and I (NC),C=C (CN) to ( R2N),P (S)CENNP ( NR,) (R=i-Pr) gives ( R2N),P=N1 N=C[P(S) (NR,),]C(CO,Me)=&(CO~e,) and (R,N),P=NN=C [ P (S)(NR,) ,] C [ C (CN)=C (CN),] =h respectively.19’ The reaction of (NPC1,) NCCl with aryloxide ions gives [ NP (OC,H,X) ,] NC (OC,H,X) (X=H, CMe,, CMe2Ph, OMe, Ph, CO,Me, CF,) .198 The remainder of the new reports in this area involved metallacyclophosphazenes. The Me,MN=PPh,CH,PPh, (M=Si, Ge) ligand can coordinate to both early and late transition metals at two sites, i.e., the nitrogen center (with or without Me,M removal) and the phosphine center. In that way monophosphazene cyclic materials SiMe,) =PPh,CH,hPh, (M=Mo,W) , such as (CO)&fi( Cl,$dN (MMe3)=PPh,CH,hPh, (M=Si, Ge) , (COD)MN=PPh,CH,PPh, (M=Rh, Ir-, COD=cyclooctadiene) and C1 (CO)RhN (MMe,) =PCH,$Ph, can be formed.84 The combination of early and late metals in the same species can also be achieved. The Me3SiN=PPh2CH2EPh2(E=P, As) i provides a core for construction of C1,Ti (Cp)h=PPh,CH,EPh,PdCl, ( Cp=qS-C,H,) by two routes, from the linear phosphazene containing the CpTiC1, unit by addition of PdCl,(CH,CN), or from the cyclic palladium complex by addition of CpTiCl3.lW The LiCH2PPh2=NR (R=C6H,-p-Me) reagents reacts with (ML2C1) dimers to give 2 8 (M=Rh, L=COD, CO; M=Ir, L=COD).200-201Reaction of 2 8 (M=Rh) with HC1 leads to disruption of the metallacycle by Rh-C bond cleavage.,O0 The acyclic diphosphazenes, CH, (PPh,=NR) (R=C6H4X; X=Me, OMe, NO,), combine with the aforementioned (MhC1) dimers to give a mixture of (L,hNR=PPh,CH,PPh,=hR) +C1and [ L 2 M w C H ( P P h 2 N R )]+C1’ the latter arising from a novel C-H to N-H hydride shift. The deprotonated form of the diphosphazene, LiCH ( PPh2=NR) gives L,MNR=PPh,CH (PPh,=NR) . The reaction of (Me,Si) ,NPPh2NSiMe3 with ZrC1, gives More complex metallacycles are C1,irN (SiMe,) PPh,=kSiMe,. obtained from TiC1,/Ph2P(=NSiMe3) OSiMe, and 1 C13V=NSiMe,/PhzP (Cl)=NSiMe, which give Cl,d?iOPPh,NTi (Cl,) OPPh,N and Cl,;NPPh,NV (Cl,)NPPh2h respectively. An unexpected ring 1 atom exchange reaction occurs when C13do=N-PPh2=N-PPh2Nreacts with Ph3SiOH and C1202MoOPPh2NHPPh20is obtained. A direct route to this compound is from C12Mo02 and O=PPh,N=PPh,OH. If Me3COH is used in place of Ph,SiOH a monophosphazene,
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Organophosphorus Chemistry
C1 (O)doOPPh,=NPPh,b is obtained which is shown by ESR spectroscopy to exhibit little ligand-metal delocalization. A direct route to this complex is from the reaction of MoOC13 with Na[OPPh,NPPh,O]. Oxidation of the complex gives the dioxo species O,doOPPh,=NPPh,b. ,02 Similar chemistry occurs when C1,V=NPPh2=NPPh,=N is allowed to react with Me3COH, Me3COLi or Ph3SiONa and a low yield of O=+-[OPPh2N=PPh2a]2 is obtained. The ESR spectrum of this d' complex does not show any resolved 31 P hyperfine coupling again indicating low degrees of metalligand delocalization. The complex may be prepared directly from VOC1, (THF) and 2Na (OPPh,NPPh,O) ,03 Another novel reaction occurs when MoOC1, is treated with (H2NPPh2NPPh2NH2)+C1and in addition to the expected Cl,ho=NPPh,=NPPh,=k, Cl,M6 (=NPPh,=NPPh,b) is obtained.,03 The reaction of NaN [ P (0) Cl,] with Me3SiC1 gives Me3SiOPCl2=NP(0) C1, in which trimethylsilyl group exchange between oxygen atoms is seen in the low temperature 31PNMR spectrum. This silyated derivative reacts with MC1, to give h(OPCl,NPCl,b), (M=A1, Gar In) , with Me,SnCl, to give Me,SA (OPCl,NPCl,O) and TiC1, to give I The titanocycle is also available from C1,Ti (OPC12NPCl,b) LiN[P(O) Cl,] .,04 Formation constants for LN(N[P(O) (OEt)2]2)3 have been obtained.,05
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,.
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6 Polv (DhosDhazenes)
This section is devoted to polymers containing open-chain phosphazenes and related cross-linked materials. Cyclolinear and cyclomatrix phosphazene polymers are covered in section 3 . A review of the preparation, properties and uses of poly (phosphazenes) is available.206 Additionally several brief , focused reviews of the following topics have appeared: the role of side groups on the ability of cyclophosphazenes to undergo polymerization"' , the role of the leaving group on polymerization vs cyclization in the thermal decomposition of Me,SiN=P (X)R, , anionic polymerization of phosphoranimines to linear phospha~enes~~', polymers obtained from functionalization of anions derived from deprotonation of { Ph(Me) PN]n208J209r preparation and characterization of liquid crystalline poly (phosphazenes),lor use of poly (phosphazenes) as drug
337
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controlled release"' and biodegradable materia1s2l2 and two less accessible reviews of poly (phosphazene) chemistry.213'214 The replacement of N into the PO, tetrahedron to yield nitride phosphates has been reviewed.215 The synthesis of poly(phosphazenes) from small molecular precursors continues to attract attention. Polymerization of N,P,Cl, by a catalyzed solution process yields high molecular weight with a narrower molecular weight distribution than that obtained from bulk polymerization.2'6 New elastomers have been obtained from the bulk homopolymerization of N,P,F,R (R=CMe,, Ph) , 2 ,4-N,P3C1,R2 (R=Me, Et) and (NPClMe) and copolymerization of (NPClR), (R=Me, Et) with N,P,Cl,. After derivatization with OCH,CF,, a series of elastomers with Tg ranging from -40 to -60' were ~btained."~Similar polymerization reactions of N3P3C1,0Ph alone and with N3P,C1, (OPh) occur.218 Poly (phosphazenes) with defined short chain linear phosphazene branches are obtained when 2,2N,P,Cl,(N=PCl,), is heat to 150' for two hours. Derivatization with oxyanions preferentially takes place at the side chain allowing for synthesis of (NPCl,NP[N=P(OR),],), and ( NP (OR),NP [ N=P (OR), ],) , ( R=CH2CF3, Ph) .133 The ring-opening polymerization of N3P3(NCS), leads to low molecular weight [NP(NCS),In polymers.219 Anionic initiation of (CF,CH,O) P=NSiMe, polymerization by BU,NF gives essentially a quantitative yield of [(CF,CH,O),PN],, PTFE, at temperatures below 100'. A narrow polydispersity (1.52) is observed.220'221 Heating of [NP(NH2)2]3,4leads to a material proposed to be [NP(NH2),In although previous work suggests the formation of imidophosphazenes.'19 Interest in heterophosphazene polymers I first noted last year, continues. The ring-opening polymerization of (NPCl,),NCCl occurs at 120- to yield [(NPCl,),NCCl], which maybe derivatized to a series of hydrolytically stable aryloxy polymers, [NP(OAr)2NC(OAr)],. Glass transition temperatures of these materials are 16 to 42O higher than the corresponding [NP(OAr)2]n analogs. No Tm Similar treatment of (NPC1,),NS (0) C1 process was observed.19* gives [(NPC12),NS(0)C1], which can be derivatized sequentially by phenoxide with the EPC1, centers being more reactive.222 The reaction of Li,N with P,N, gives pure LiPN, which exhibits
,,,
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,-
338
Organophosphorus Chemistry
corner sharing PN, tetrahedra.223 Ammonolysis of (NaP03) gives phosphorus oxynitride glasses. The UV/Vis spectra of these glass with Pb2+,Nd3+ and Eu3+ probes allows for the suggestion that the nitrogen atoms are inserted between phosphorus atoms in the metaphosphate chains.224 The synthesis of poly(phosphazene) derivatives by single or multistep reactions of preformed polymers allows for the construction of otherwise unavailable polymers. Some of these reactions have been described above. High molecular weight [NP(NSC)2]n is obtained by metathesis from the chloropolymer. Reactions of the isothiocyanato polymer with alcohols leads to partial formation of thiourethenes while reactions with amines lead to complete conversion to thiourea side groups. Mixed substituent alkoxy-thiourea or thiourethane polymers also can be Vulcanization of (NPRR') (R=NHBu; R'=NHBu, NEt,) with isothiocyanato poly(phosphazene) derivatives is more effective than with OCN (CH,),NCO. 225 Preparation of [NP(NHBu)x(OPh)2-x]nand vulcanization with hexamethylene diisocyanate has been reported.226 Poly (phosphazene) derivatives of the sodium salt of diacetone D-glucose alone or mixed substituent (NHMe, OPh , OCH2CF3, OCH,CH,OCH,CH,OMe) derivatives can be prepared and converted to the free glucose containing polymers by acid hydrolysis of the protecting group.227 Mixed substituent polymers containing viologen side chains linked to the phosphazene chain by alkoxy residues have been patented.,'* Enantiotropic liquid crystallinity is observed in poly(ph0sphazenes) bearing biphenyl mesogenic groups which are obtained from (NPCl,), and the ethyleneoxy derivatives 0(CH,CH,) ,OC,H,C,H,R. '39 Liquid crystalline poly (phosphazenes) containing 0 (CH,),0C6H,C6H4CN229 , OC6H4C02R (R=Bu, amyl , decyl) 230 and OCH,CH,0C6H,N=NC6H,C,H,231 substituents have been prepared and characterized. Azoxybenzene units with chiral alkoxy terminal units have been introduced as poly (phosphazene) side chains.232 Photochromic spiropyrans have linked to poly(phosphazenes) through oxomethylene spacers, O(CH,CH,O),O (n=2,3). Solid state or solution photolysis reversibly generates merocyanine group.233 Primary amino acid groups protected by N-tert-Butylcarbonyloxo (BOC) groups can be coupled to the phosphazene via a O(CH,),O spacer. Sequential
8: Phosphazenes
339
deprotection and amide formation allows contruction of tripepiptide side chains (see section 3 ) Aminoacid esters with quaternized amines react with (NPCl,), to give the aminoacid ester derivatives.234 The synthesis of a wide range of polymers having the composition [ NP (OCH2CF3)(OR), 3 (R=O(CH,CH,O) ,C6H4(CH=CH),,,C6H,A; k, m=1-3 A=N02, CN) have been prepared and exhibit non-linear optical activity.135 The synthesis of [NP(OC6H,C(0)OEt),], followed by hydrolysis to the free acid, [ NP (OC,H,CO,H) ,] , gives a polyelectrolyte which can be crosslinked with polyvalent cations to give hydrogels. These hydrogels are the first synthetic polymers which can be used for encapsulation of cells, liposomes and proteins. Encapsulated liver cells retain their activity.235 Poly(phosphazene) electrolytes for solid state ionic conductivity have been obtained as metal salts of 01 i g o a l k y l e n e o x y p h o s p h a ~ e n e s ' ~ ~ 'and ~ ~ ~from ' ~ ~ ~ the lithium salts238 of sulfonated aniline functions prepared by the reaction of [ NP (NHPh),] ,with HS03C1.239 Surface reactions of poly(phosphazenes) have attracted attention this year. The reactions of solid PTFE with Na(OCH2CH2),R (R=OH, CN, NH,) induces displacement of trifluoroethoxy groups at the surface by the nucleophiles to more hydrophilic surfaces. The surface hydroxyl and amino group can be further functionalized by reaction with phenylisocyanate.240 Similar reactions of commercial fluoroalkoxy phosphazene rubber materials have been reported.241'242 Surface hydrolysis of PTFE with NaOH/Bu,NBr gives surface-O-NB; groups leading to adhesive properties. Cations can bind to the modified surface. Similar chemistry on aryloxy derivatives was explored.243 Plasma etching by atomic oxygen has been applied to phosphazene films. Significant backbone changes occurring in fluoroalkoxy derivatives.244 In a comparison of OCH2CF3, OEt , NHPh, NHC,H,Cl , OPh and OC6H,C1 derivatives the aromatic amine and phenoxides were more resistant with the bisanilino derivatives exhibiting stability similar to Novolak resin.245 Finally, [NP(OCH,CH,OCH,CH,OMe) ,In (MEEP) may be entrapped in poly(methylmethacry1ate) which is crosslinked with dimethylacrylate or poly(styrene) crosslinked with divinylbenzene to give the first characterized phosphazene containing interpenetrating polymer networks.246
340
Organophosphorus Chemistry
Physical measurements and calculations on poly(phosphazene) systems are an important ongoing area of concerns. Ab initio MO calculations on short chain models H,P(NPH,),NH suggest that internal bond length alternation continues to the high polymer level.’, A combination of Huckel and third-order perturbation approaches allowed for calculation of the 3rd order hyperpolarizability, for (X,PN),. The effect, which is comparable in magnitude to organic polymers, is dependent ligand electronegativity and relates to the n orbital energy difference between phosphorus and nitrogen.247 The second harmonic generation ability of poly(phosphazenes) is claimed to be related to substituent polarization and hence the ability to design desireable properties by substituent modification.248 The bond polarity indicated above does not preclude understanding of electronic structure in terms of molecular symmetry.” CNDO/1 methods have been used to calculate vertical ionization energies and electronic absorption energies. Experimental ionization energies, as measured by XPS, have been shown to relate directly to the polarizability of the PN bond which is more significant in the polymers than in cyclic systems. lo4 ESCA measurements have been used to evaluate surface effects of atomic oxygen The presence of surface modifications of PTFE reactions from treatment by nucleophiles was established by a battery of methods (XPS, SEM, TEM, ATR-IR and contact angle measurements) .240 According to XPS data, the concentration of N is lower on the surface than in bulk for PON, PON-P,N,, (PON)(P,N,) .75 , P,N, , (PNH,) (P,N,) .4 and PN,H 249 Electronic spectroscopy of poly[bis(P-naphthoxy)phosphazene] has been studied. No naphthalenic triplet-triplet absorption or phosphorescence was observed and the behavior of the polymer is significantly different from the trimer in both solution and rigid matrices. lo5 The microenvironment created by { [NP(Me) Ph] (NPPhCH,CO,H) ) ” in aqueous solution was examined using three different fluorescent probes. The polarity at high pH was similar to MeOH. The phosphazene can bind positively charged ions and repel negative ions.250 FT-Raman spectra of samples [NP(OC,H,Me)2] with different thermal histories were related to the crystalline and mesophase content of the .2441245
.
8:
Phosphazenes
341
materials .251 Cross-linked phosphazenes can be oriented in an electric field to give materials with excellent piezoelectric properties.252 Second-harmonic generation by (NP( OCH2CF3) [ 0(CH,CH,O) ,C,H, (CH=CH),C6H,H] 2-x ) films is achieved by application of electric field. The 2nd-order non-linear coefficients were determined and related to polymer composition and structure.13’ Morphological and related studies have been carried out on numerous systems. The effect of different production technologies on Tg, temperature of the secondary relaxation and m.p. of crystalline phases of PTFE has been studied.253 The thermal history of samples of [ NP(OC,H,Et) ,In strongly effects the formation of the crystalline state and its morphology as shown by small-angle light scattering and polarized microscopy during the transitions from the crystalline to the mesophase and on to the isotropic melt.254 Phases available to PTFE by changes in annealing temperature have been probed using DSC.255 A detailed study of the liquid crystalline behavior of [ NP (OCH,CH20C6H4N=C6H,C4H9) ,] by DSC, polarized optical microscopy and x-ray diffraction has appeared. Semetic A and C phases were detected and related to structural features involving the side chain.23’ The PTFE crystal-mesophase (T,) and mesophase-isotropic phase (T,) transitions have been studied as function of added solvent (DMSO and ethylacetate). DMSO lead to decreased T, until 5% DMSO when the mesophase disappeared and T, and T, merged.256 Electronmicroscopy of ultrathin PTFE films showed a radical effect of solvent (heptane, dioxane, DMSO, C2C1,) on morphology. T, was decreased by some solvents providing a mesomorphic transition at a lower temperature than the initial T,.257 Features of flow and structure of PTFE-high density polyethylene (HDPE) blends were studied by thermochemical, xray, electron microscopy, and rheological methods. Viscosity of blends is close to PTFE viscosity or below it. A specific morphology having PTFE fibers in the HDPE matrix surrounded by a poly (phosphazene) shell was proposed.258 Polyethylene with 10% PTFE exhibits a 3.5 fold decrease in melt viscosity due to concentration on the extrudate surface and behaving as a low viscosity lubricant.259 The conformationally disordered state of the PTFE mesophase has been related to these effect^.^^'-'^'
342
Organophosphorus Chemistry
The phase transitions in [ NP (OC,H,R) 2] (R=OMe, SMe) were studied by DSC, x-ray diffraction and optical microscopy. The substituent effect on thermal transitions and mesophase formation in these and related polymers have been analyzed. A significant dependence of the crystallization kinetics on the temperature of the mesophase in I and I1 was noted.',' The azoxy group suppresses side-chain crystallization in poly(phosphazenes) with azoxybenzene derivatives having chiral alkoxy terminal units as side chains. The thermal behavior depends on spacer group length and morphologies were proposed from consideration of x-ray data.232 Gas permeation of 13 gases in PTFE above the mesophase (T1)transition were measured. Notable changes above and below T, are observed and proposed to relate to gas ( C 0 2 ) dispersion in the rnesophase.262 The gas permeability and selectivity for poly(phosphazene) membranes show that [NP(OC,H,Et),], had the highest N, H selectivity while PTFE had the highest CO,, He selectivity. Dielectric constant is an important parameter in increasing gas permeability.263 Phosphazene thin film electrolytes continue to be studied extensively. Electrochemical stability of MEEP,LiSO3CF, has been carefully studied. Diffusion constants for solutions of electroactive activity solutes such as ferrocene in this system have been obtained.264 Mixed MEEP poly (propyleneoxide) LiX electrolytes have been evaluated and found to be amorphous with increased dimensional stability and slightly decreased conductivity.265 MEEP blends containing LiC10, or LiBF, have also been studied by 7 L i NMR. Significant cation mobility occurs only above the lowest Tg.'& The CO dependent solid state electrochemistry of 10 combined with MEEP/LiCF,SO, has been studied.78 The storage power of [ NP (NHPh)1.26 ( NHC6H4S03H). 7 4 ] (which could be repeatedly charged and discharged) was determined.239 Solid state conductivity and transference numbers for numerous other oligoalkyleneoxyphosphazenes have been reported.138.236-238.267 Thermal degradation of poly (phosphazenes) has been examined using 31PNMR, gas chromatography and mass spectrometry to evaluate the products.268 PTFE undergoes random chain cleavage followed volatilization of cyclics. Aryloxy species followed a similar path and also exhibited cross-linking. Cross-linking was the
8: Phosphazenes
343
exclusive mode for alkylamino, ferrocene or ruthenocene derivatives.268 Additional products were observed for [NP(OPh)2], including triphenylphosphate, aniline and phenylaminophosphates.'ol The effect of steam hydrolysis on phenoxy derivatives with variable degrees of residual phosphorus-chlorine bonds was examined.'08 The optical properties of various poly(ph0sphazene) thin films on silica or silicon were determined. The effect of laser damage to the films was related to substituent groups on the polymer."' Solution characterization of poly(phosphazenes) have received less attention this year. Two samples of [NP(OEt)2], with significant different mo3.ecular weights were characterized by light s~attering'~' and viscometry along with GPC.271 Classical parameters such as Mark-Houwink coefficients, unperturbed dimensions and 2nd viral coefficients were calculated. The Kerr constants for PTFE solutions are available and were 3 to 4 orders higher than those for flexible chain macromolecules. The high polarity of the chain depends on the dipole moment of the monomer unit.272 The heterogeneity and kinetic stability of PTFE solutions are influenced by molecular weight, solution concentration, and polymer chemical modification but not by solvent.273 High-performance size-exclusion chromatograph, gradient reversed-phase HPLC and ion chromatography were used to characterize the water soluble, biodegradable, poly (chloromethoxytrialanine methyl ester phosphazene) .274 A significant volume of applications oriented material is available indicating the ongoing commercial interest in these materials. A significant number of these relate to solid state conductivity applications in which variations on batteries typically having a lithium anode, metal oxide cathode and electrolytes made of various oligoexyethylene/poly(phosphazenes) combined with ionic salts.275-280 Poly(phosphazene) films containing oxyethelene side chains have several desirable properties such as antistatic, hardness, transparency, etc., which makes them suitable for photographic materials.281-283A particularily noteworthy system is a blend of MEEP and silica obtained by the sol-gel process.284 Phosphazene photoresists based on PTFE and related material^'^' or side chains containing carbonyl groupszw have been reported.
344
Organophosphorus Chemistry
PTFE has also been used as a component of a membrane light modulator. Surface modification chemistry of PTFE has been used for surface property improvement.288 Blends of commercial poly(ph0sphazenes) (Eypel A) and organic polymers are suitable for low-smoke and fire resistant coatings.289 Protein fibers, e.g. silk, can be shrink proofed using amidophosphazene resins.290 Biological applications have also attracted attention in areas such as controlled release of active agentsZ9’ 292 and marine antifouling.293 7 Molecular Structures o f PhOSDhaZeneS
The following structures have been determined by x-ray diffraction. All distances are in picometers and angles in degrees. ComDound
Comments
Me,S iNPPh,CH,PPh,
PN 152.9(3); LNPCH2 116.6 (1)
(RN),CN(Me) PPh,.CHCl, (R=l,2,4 triazene)
7 PN 166.2(3); LPNCR,123.1(2) weak, long distance P.. .N
(RN)2CN (Et)PPh3*1/2 C,HaO, R=1,2,4 triazene)
PN 165.6(4); f PNCR, 123.5(3)
7
(RN),CN(n-Pr) PPh3*2CHC1, (R=1,2,4 triazene)
L PNCR, iig.i(6)
PN 165.1(8);
7
PN 154.9(2);
30
PN 154.1 (2); PNCSi, 143.99 (9)
30
4-CF,C,H,C [ N ( S iMe,) 3 NPPh,NS iMe,
P=N 154.5 (3) : PN 166.8(4)
33
4-Me,NC,H,C (NSiMe,) N ( S iMe,) PPh,NS iMe,
P=N 154.8(7): PN 165.2(6)
33
2 , 4 ,6- (Me,C),C,H,NP ( CMe,) C (SiMe,)
2,4,6(Me,C),C,H,NP[
2
(X=NMe,, R=Ar=Ph)
16
.
,
,
(Me,C),C,H,] C (SiMe,)
(Me3C),PP (NMes)NCEt, Mes=2,4,6-Me3C,H,
Ref.
L PNCSi2 133.39 ( 8 ) L
PN=153.1(4) : 153.7 (4) L N=P=N 139.7 (2) N,P, ring and NPh coplanar P=N 151.8
29 20
345 s l i g h t l y d i s t o r t e d 80 from p l a n a r : c i s / t r a n s backbone PN 152.4(13), 153.3(13), 157.1(14) LPN,P 142.6: L PN,P 127.8 ( C13PNPC13)+VOCl,-
PN 157(2), 152 (2) LPNP 138(2)
294
R h (COD)C 1 (RN=PEt3) R=p -to 1y 1
NRh c o o r d i n a t i o n PN 160.8(3): LRhNP 121.0
92
PN 157.3(3), 157 ..2(3) PNH, 162.4(2); LP=N=P 142.9
69
PN=160.5 (16): L PNRe 180.0(1)
90
(NH,PPh,NPPh,Me) +C1'
Ph3P=NRe(NR) R=2,6- ( i - p r ) ,C,H3 ( 03ReNPPh,) ,C,H,
SeC1, [ NPPh,NS ( 0 )Me,]
,
Ph3PNNbC13( vS-C5Me4Et) [ (v-'C,Me,Et)
NbCl,NPPh,] C,H,
PH,Cl, [ (CF,) ,PNPPh3]
PN 157.2(7);
85
PN(Se) 158.9(9), 163.5 (9) PN(S) 162.7(9), 161.1(9)
89
PN 160.0(3);
88
L PNRe 154.1 (3)
L PNNb 168.5 (2)
PN 159.3(3); L PNNb 172.8(2)
88
(-3) ,PPd 93 coordination; PN 155.9(6), 158.3(8) LPNP 143.4(5)
(CF3) ,pas 94 coordination; PN 155.5(15), 155.3(15) LPNP 175.4(12) PN,, 157.5 (2)158.8 (2) . . PN(Me,) 161.7(7), PN (CS) 169.0 (9)
118
p l a n a r ; PN,,, 113 165.7(6), 165.6(5) PN,, 155.9 (5)-160.3 (7)
Organophosphorus Chemistry
346 2,cis-4,trans-6,trans-8-
non-planar ; PN,,, 161.8 (mean) PN,, 156.1 (mean)
14 (n=2)
planar N3P3 ring 122 trans t o 30 membered (chair) ring; PN,, 156.0 (5)-159.9 (5) PN,,, 161.1(5) 161.5(4)
N,P, ( N E t , )
,c1,
29 5
N,P, rings trans 124 to chain; PN,, 154.8 (8)-161.1 (8) PN,,, 159.4 (8): NH....OH bond
trans bridge 125 PN,, 154.9 (5)-160.5 (5) PN,,, 158.3 (5), 158.4 (6) N3P3 slightly 80 puckered ; P N 155.4 (7)-160.2 (7) L N P N 115 1 ( 4 ) - 118 0 ( 4 ) L P N P 120.9 (5)-123.2 (4)
.
.
boat; 80 P N 152.9 (9)-157.1(8) L P N P 132.1(6) -138.7 (6) 1 N P N 119.5 (5)-121.4 (5) P N 157.4(1), 129 158.3(1) I 157.9(1) L P O P 128.8(2) I 135.5(2) [ N P (OPh)2 ] ,NP ( 0 )OPh
boat ; P N 154.6-160.7
296
P3N3 147 essentially planar: P N 156-160 1 SPS 109.4(1) I 109.2(1)
21eTHF
N3P3 ( C H 2 S iMe3)6
distorted chair:
L N P N 116.5
149
PN 158.0 (5)-161.6 (5)
2 I 2 -N,P,Cl,
( CH2S iMe,) ( CMe,)
puckered chair; 148 P N 155.1(1) -162.0 (1) L C P C 108.85(9) ; L N P ( C 2 ) N 113.94(7)
2 I 2-N,P,Cl,
( C H 2 S iMe,)
puckered chair: 148 P N 155.0 (2)-163.5 (1) L C P C 107.9(1) ; L N P ( C 2 ) N 113.09 ( 8 )
347
8: Phosphazenes PN(mean) 1 6 2 . 7 ( 6 ) , 154.6(4) , 158.0(4) f CPC 9 5 . 1 ( 2 ) ; LNP(Cz)N 1 1 2 . 8 ( 3 )
22
N,P,F,C,H,
q6-Cr
(co)
150
PN 1 5 5 . 3 ( 5 ) 160 157.0(4) PFR 1 5 5 . 4 ( 3 ) ; PF, 1 5 2 . 1
,
LiN30,
(N,P3C1,RLi) R=NH (CH,) 3O (CH,) ,O (CH,) ,N
156
coordination;
P3N3 p l a n a r PNexo 1 5 8 , 166 PN, 154-165 156
ZnN302 coordination; d i s t o r t e d N3P3
156 6 coordinate Mg, includes endocyclic N; N3P3 h a l f c h a i r PN, 154-170 PNexo 161-6
(N,P,Cl,~g) 2 R=N (CH,) 0 (CH,) ,O (CH,) 3N
29
297
'endo
1 5 8 . 2 ( 9 ) -164.5 ( 9 ) PNexo 1 6 3 . 2 (10) 166.4 (11)
-
Two S atoms 187 d i s p l a c e d from P,N, p l a n e ; PN 1 6 2 . 2 ( 5 ) , 1 . 6 1 4 ( 4 ) ; L NPN 1 1 9 . 7 ( 2 )
23 (E=S)
26
(R=R1=Me,
R1'I=NOZ, R"I1=C1)
27
(R=R'=Me,
R"=NO,,
(R?N) ,+NNC [ P ( S ) (NR,) R=i-Pr
R"'=H)
,3
C ( C0,Me)
1
C 1 3 Z k N (SiMe,) PPh,NSiMe,* CH,CN
C1,T iOPPh,NT i Cl,OPPh,N
4 CH,CN
2 8 (M-Rh,
IiCOD)
1
R=p-tolyl,
o n l y minimal data given
193
o n l y minimal
193
d a t a given
t ( C0,Me)
n e a r l y p l a n a r r i n g 197 PN, 165.6 ( 4 ) PN,,,, 1 6 4 . 0 ( 3 ) , 1 6 4 . 2 ( 3 ) 'endo
161.5(5) , 160.0(5) C NPN 1 0 0 . 5 ( 2 ) ( e n d o )
21
nearly planar 21 8 membered r i n g ; PN 1 6 0 . 5 ( 2 ) s h o r t T i N ; l a r g e f PNTi PN 1 6 2 . 4 ( 2 ) ACPN 9 9 . 1 ( 2 )
200
348
Organophosphorus Chemistry I -
,
ClzOzMoOPPPh,NHPPhzd* THF
PN 1 6 5 . 5 ( 1 2 ) 165.7 ( 1 2 ) LPNP 1 2 3 . 2 ( 6 )
2 02
ClOMoOPPh,NPPh,O
PN
159.6(5) 159.6 ( 6 ) LPNP 1 2 5 . 7 ( 4 )
202
PN
202
159.1(2) 157 ( 3 ) LPNP 1 2 5 . 3 ( 2 )
O$ ( OPPh2NPPh2b) r
1
ClzMO(OPPhZNPPhzN) 3CH3CN
PN
158.9(2), 203 158.6(2) , 159.2(2) 123.7(1) , 124.2(1)
LPNP PN
156.4(14)157.6(12); 165.4 ( 8 ) -164.0 ( 7 )
203
chelate via P=O; PN 1 5 7 ( 2 ) - 1 5 3 ( 2 )
298
first triply bridging phosphoranimine PN 1 6 0 . 9 ( 7 )
36
1 5 5 ( 2 ) -150 ( 2 )
5
LiPN,
References 1. 2. 3. 4. 5.
6. 7.
8. 9. 10. 11.
PN, Td; PN 1 6 4 . 5 ( 7 ) ; L PNP 1 2 3 . 6 ( 8 )
223
Phosahorus, Sulfur Silicon Relat. Elem., 1990, 4 9 - 5 2 . J. Barluenga and F. Palacios, m. PreD. Proced. Int., 1991, 23, 1. Y. Lino and M. Nitta, J. Svnth. Ora. Chem. JaDan, 1990, 48, 6 8 1 . C.E. Davis, R. Hani, D.L. Jinkerson, P. Murkerjec, G.M. Scheide, C.E. Wood and R.H. Neilson, Phosphorus, Sulfur Silicon Relat. Elem., 1990, 51-52, 1 6 1 . E. Niecke and D. Gudat, Anqew. Chem., Int. Ed. Enql., 1991, 30, 2 1 7 . P. Pyykko and Y. Zhao, Mol. Phvs., 1990, 70, 7 0 1 . P. Molina, M. Alajarin, C.L. Leonardo, R.M. Claramunt, M.C. Foces-Foces, F.H. Cano, J. Catalan, J.L. G. dePaz and J. Elguero, J. Am. Chem. SOC., 1989, 111, 3 5 5 . P.V. Sudhakam and K. Lammertsma, J. Am. Chem. SOC., 1991,
113, 1 8 9 9 .
A.A. Korkin and A.M. Mebel, Metalloors. Khim.. 1990, 3, 1 0 0 5 (Chem Abst., 1991, 114, 1 0 2 2 0 9 q ) . A.A. Korkin, Int. J. Ouantum Chem., 1990, 3 8 , 2 4 5 . K.F. Ferris, S.M. Risser and A.K. Hanson, Mater. Res. SOC. SvmD. Proc., 1990, 173 (Adv. Org. Solid State Mater), 6 8 3 (Chem. Abst., 1990, 113, 1 5 3 3 6 0 ~ ) .
8: Phosphazenes
12. 13. 14. 15. 16. 17. 18. 19. 20. 21.
22. 23.
24. 25. 26. 27. 28. 29. 30. 31. 32.
33. 34. 35.
36. 37. 38.
39.
349
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H.W. Roesky, R. Hasselbring, J.Liebermann and M. Noltemeyer, Z. Naturforsch.. B: Chem. Sci., 1990, 45, 1383.
R.D. Hund and G.V. Roeschenthaler, Chem.-Zta., 1990, 114, 356 (Chem. Abst., 1991, 114, 143559x1. R.D. Hund and G.V. Roeschenthaler, Chem.-Ztg., 1990, 114, 358 (Chem. Abst., 1991, 114, 143560r). H.-F. Klein, S. Haller, H. Konig, M. Dartiquenave, Y. Dartiquenave and M.-J. Menu, J. Am. Chem. SOC., 1991, 113, 4673. H. Trabelsi, E. Bollens and A. Cambon, Svnthesis, 1990, 623. N.G. Zabirov and R.A. Chenkasova, J. Gen. Chem. USSR [Enal. Transl.) , 1990, 60, 1116. N.G. Zabirov, F.M. Shamselvaleev and R.A. Cherkasov, J. Gen. Chem. USSR (Enql. Transl.), 1990, 60, 464.
Organophosphorus Chemistry
350 40.
M. Yu. Dmitrichenko, G.V. Dolgushin, V.G. Rozinov and V.I. Donskikh, J. Gen. Chem. USSR (Ensl. Transl.), 1990, 60, 401.
42.
H. Hund and G.V. Roeschenthaler, Chem. -Zts., 1990, 114, 386 (Chem. Abst., 1991, 114, 185638~). V. Yu. Kukushkin and A.I. Moiseev, Inors. Chim. Acta,
43.
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231. R.E. Singler, R.A. Willingham, C.Noel, C. Friedrich, L. Bosio and E. Alkins, Macromolecules, 1991, 2 4 , 510. 232. H.R. Allcock and C.Kim, Macromolecules, 1991, 24, 2841. 233. H.R. Allcock and C. Kim, Macromolecules, 1991, 24, 2846. 234. E. Schacht and J. Crommen, US 4965397 (Chem. Abst., 1991, 114, 186066b). 235. S . Cohen, M.C. Bano, K.B. Visscher, M. Chow, H. R. Allcock and R. Langer, J. Am. Chem. SOC., 1990, 112, 7832. 236. L.A. Dominey, T.J. Blakley and V.R. Koch, Proc. Intersoc. Eneruv Convers. Enq. Conf., 1990, 25th Vol. 3, 382 (Chem. Abst., 1991, 114, 105617g). 237. T. Nakanaga, Y. Tada and A. Insubushi, JDn. Kokai Tokkvo Koho, JP02169628 (Chem. Abst., 1990, 113,232301d). 238. Y. Kurachi and M. Kajiwara, J. Mater. Sci., 1991, 26, 1799. 239. Y. Kurachi, K. Shiomoto and M. Kajiwara, J. Mater. Sci., 1990, 2 5 , 2036. 240. H.R. Allcock, R.J. Fitzpatrick and L. Savati, Chem. Mater., 1991, 3 , 450. 241. C.H. Kolich, W.D. Klobucar and J.T. Books, US49413A (Chem. Abst. , 1990, 113, 154152q). 242. C.H. Kolick and W.D. Klobucar, US4945140 (Chem. Abst., 1990, 113, 1541333). 243. H.R. Allcock, J.S. Rutt and R.J. Fitzpartick, Chem. Mater., 1991, 3 , 442. 244. L.L. Fewell, J. ADD^. Polvm. Sci., 1990, 41, 391. 245. M. Kajiwawra and Y.Yamashita, J. Mater. SCi., 1991, 26, 2797. 246. K.B. Visscher, I. Manners and H.R. Allcock, Macromol., 1990, 23, 4885. 247. S.M. Risser and K.F. Ferris, Chem. Phvs. Lett., 1990, 170, 349. 248. G.J. Exarhos and W.D. Samuels, Mater. Res. SOC. SvmD. Proc., 1990, 175,95 (Chem. Abst., 1991, 114, 248193b). 249. V. Avotins, J. Sulga, A. Vitola and T.M. Moravshaya, Ltv. PSR Zinat. Akad. Vestis, Kim. Ser., 1990, 285 (Chem. Abst., 1990, 113, 223674a). 250. C.E. Hoyle, P. Wisian-Neilson, P.M. Chatterton and M.A. Trapp, Macromolecules, 1991, 2 4 , 2194. 251. G. Ellis, M.A. Gomez, C. Marco, J.G. Fatou and R.G. Haddon, Polvm. Bull. (Berlin), 1991, 2 5 , 351. 252. T. Kotaka and K. Adachi, US4933479 (Chem. Abst., 1990, 113, 2229352). 253. A.V. Semakov, E.K. Borisenkova, B.S. Khodyrev, D.R. Tur and V.G. Kulichikhin, Vvsolkomol. Soedin.. Ser. B., 1989, 3 l , 830 (Chem. Abst. , 1990, 113, 416383). 254. M.A. Gomez, C. Marco, J.G. Fatou, S.V. Chichester-Hicks and R.C. Haddon, Polvm. Commun., 1990, 31, 308. 255. A.T. Kalashnik, G. Ya. Rudinskaya, S.P. Papkov, L.K. Golova, N.P. Krachinin, N.V. Vasileva and D.R. Tur, Vvsolkomol. Soedin., Ser.A., 1990, 3 2 , 1053 (Chem. Abst., 1990, 113, 60307s). 256. L.K. Golova, G.Ya Rudinskaya, S.A. Kuptsov, N.V. Vasil'eva, A.T. Kalashnik, E.M. Antipov, D.R. Tur and S.P. Papkov, Vvsokomol. Soedin., Ser.B., 1990, 32, 605 (Chem. Abst., 1990, 113,232396~).
358
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257. M.M. Iovleva, N.A. Ivanova, S.I. Banduryan, G.A. Mikheleva, L.K. Golova and D . R . Turf Vvsokomol. Soedin. Ser. B., 1990, 32, 316 (Chem. Abst., 1990, 113, 60519n).
258. E.K. Borisenkova, D.R. Tur, I.A. Litvinov, E.M. Antipov, V.G. Kulichikhin and N.A. Plate, Vvsokomol. Soedin., Ser. A., 1990, 32, 1505 (Chem. Abst., 1990, 113, 116448h). 259. E.M. Antipov, E.K. Borisenkova, V.G. Kulichikhin and N.A. Plate, Makromol. Chem.. Macromol. SvmL)., 1990, 38, 275. 260. N.A. Plate, E.M. Antipov and V.G. Kulichikhin, Makromol. Chem., Macromol. Svmp., 1989, 33, 65. 261. M.A. Gomez, C. Marco, J.G. Fatou, T.N. Boner, R.C. Haddon and S.V. Chichester-Hicks, Macromolecules, 1991, 24, 3276. 262. K. Mizoguchi, Y. Kamiya and T. Hirose, J. Polvm. Sci., Part B: Polvm. Phvs., 1992, 29, 695. 263. M. Kajiwara. Sep. Sci. Technol., 1991, 24, 841. 264. R.A. Reed, T.T. Wooster, R.W. Murray, D . R . Yaniv, J. S. Tonge and D.F. Shriver, J. Electrochem. SOC., 1989, f36, 2565. 265. K.M. Abraham, M. Alamgir and R.D. Moulton, J. Electrochem. SOC., 1991, 138,921. 266. K.J. Adamic, S.G. Greenbaum, K.M. Abraham, M. Alamgir, M.C. Wintersgill and J.J. Fontanella, Chem. Mater., 1991, 3 , 534. 267. K.M. Abraham and M. Alamgir, Chem. Mater., 1991, 3 , 339. 268. H.R. Allcock, G.S. McDonnell, G.H. Riding and I. Manners, Chem. Mater., 1990, 2, 425. 269. G.J. Exarhos and K.M. Crosby, NIST SDec. Publ., 1990, 801, 324 (Chem. Abst., 1991, 114, 217403r). 270. J. Bravo, M. P. Tarazona, A. Roig and Y.E. Salz, Anal. Quim., 1991, 87, 27. 271. M.P. Tarazona, J. Bravo, M.M. Rodrigo and E. Salz., Polvm. Bull., 1991, &, 465. 272. E.I. Ryuntsev, I.N. Shtennikova, D.R. Tur, G.F. Kolbina, E.V. Korneeva and V.G. Kulichikhin, Vvsokomol. Soedin., Ser. B., 1990, 32, 648 (Chem. Abst., 1991, 114, 43921r). 273. V.N. Smirnova, L,K. Golova, N.V. Vasil'eva, D.R. Tur and M.M. Iovleva, Khim. Volokna, 1990, 20 (Chem. Abst., 1990, 113, 985252). 274. G. Eickhoff , G.G. Liversidge and R. Mutherarasan, J. Chromatoar., 1991, 536, 255. 275. Y. Nakacho, A. Inobushi and Y. Tada, W09010317 (Chem. Abst. , 1991, 114, 232035r). 276. Y. Nakacho, A . Inobushi and Y. Tada, S. Masuda and M. Taniguchi, W09010316 (Chem. Abst., 1991, 114, 189085t). 277. Y. Nakacho, A. Inobushi and Y. Tada, W09010315 (Chem. Abst., 1991, 114, 189084s). 278. A. Inobushi, Y. Nakacho and Y. Tada, W09007198 (Chem. Abst., 1991, 114, 105706k). 279. T. Nakanaga and Y. Tada, Jpn. Kokai Tokkyo Koho, JP020244660 (Chem. Abst., 1991, 114, 9619~). 280. S. Yasunami, Jpn. Kokai Tokkyo Koho, JP02252762 (Chem. Abst., 1991, 114, 124169d). 281. Y. Kuraki and S. Yasunami, Jpn. Kokai Tokkyo Koho, JP02304553 (Chem. Abst., 1991, 114, 196315~). 282. T. Kkubota and Y. Kuraki, Jpn. Kokai Tokkyo Koho, JP02293844 (Chem. Abst., 1991, 114, 256890s).
359
8: Phosphazenes 283. R. Matejec, R. Buescher and H. Langen, EP 377910 (Chem. Abst., 1991, 114, 196262b). 284. B.K. Coltrain, W.T. Ferrar and C.J.T. Landry, W090113223 (Chem. Abst., 1991, 114, 165903g). 285. K. Hashimoto, T. Koizumi, K. Kitagawa and N. Nomura, Jpn. Kokai Tokkyo Koho, JP02010357 (Chem. Abst., 1990, 113, 14832m). 286. M. Gleria, F. Minto and L. Flamigni, EP369398 (Chem. Abst., 1990, 113, 181450s). 287. P.B. Rolsma and J.N. Lee, ODt. Lett., 1990, 15, 721. 288. K. Ohkawa, T. Matsuki and N. Saki, US4959442 (Chem. Abst., 1991, 114, 8 3 6 8 3 ~ ) . 289. S.C. Chang, US4966937 (Chem. Abst., 1991, 114, 45169a). 290. Y. Hayashi and Y. Nomura, Jpn. Kokai Tokkyo Koho, JP02216267 (Chem. Abst., 1991, 114, 104309~). 291. H.R. Allcock, P.E. Austin and S.Kwon, US4880622 (Chem. Abst. , 1990, 113, 6 5 2 8 1 ~ ) 292. E. Schacht and J. Crommen, US4975280 (Chem. Abst., 1991, 114, 108973f). 293. K. Nanishi and H. Nakayama, US4908061 (Chem. Abst., 1990, 113, 174129r). . 294. A. Zinn, U. Patt-Siebel, U. Muller and K. Dehnicke, Z Anora. Allaem. Chem., 1990, 591, 137. 295. T. Hokelek and Z. Kilic, Acta Crvstallosr., Sect. C: Crvst. Struct. Commun., 1990, C46, 1519. 296. M. Parvez, S. Kwon and H.R. Allcock, Acta Crvstalloqr., Sect.C: Crvst. Struct. Commun., 1991, W, 466. 297. V.I. Sokol, L. Ya. Medvedeva, M.A. Porai-Koshits and I.A. Rozanov, Russ J. Inors. Chem. {Enal. Transl.), 1990, 35, 1618. 298. A.A. Dvonkin, V.A. Kalibabchuk, A.O. Gudima, V.L. Rudzevich and Yu. A. Simonov, Russ. J.Inors. Chem. (Enql. Transl.), 1990, 35, 1717.
.
Author Index
In this index the number given in parenthesis is the Chapter number of the citation and this is followed by the reference number or numbers of the relevant citations within that Chapter. Abbari, M. (1) 297 Abdelmalek, H.A. (7) 28 Abe, A. (1) 240, 241; (7) 8 Abell, A.D. (1) 236; (7) 11, 37 Abiyurov, B.D. (5) 152 About-Jaudet, E. (5) 127, 133, 225 Abraham, K.M. (8) 265-267 Abramkin, E.V. (5) 256, 259 Abramovitch, R.A. (5) 155 Absalon, M.J. (6) 247 Abunada, N.M. (8) 6 8 Abu-Ragabah, A. (8) 202, 203 Abu-Shgara, E. (8) 65 Achi, S . (5) 206 Achiwa, K. (1) 72, 90 Adachi, K. (8) 252 Adam, W. (5) 16 Adamic, K.J.(8) 266 Adamopoulos, S.G. (7) 27 Afanas’eva, A.N. (8) 183 Afarinkia, K. (4) 9; (5) 195, 196 Agback, P. (6) 244, 245 Agrawal, S. (6) 85, 203, 204 Ahlrichs, R. (1) 295 Ahmad, S. (6) 151 Ahmed, S. (8) 153 Ahuja, J.R. (1) 148 Aitken, R.A. (1) 254; (7) 12, 46 Ajo, D. (1) 59 Akacha, A.B. (5) 242 Akagi, M. (6) 303 Akashi, M. (6) 334 Akermark, B. (7) 57 Akkerman, M.A. (6) 257 Aksinenko, A.Yu. (5) 188, 303 Aksinenko, N.E. (4) 6 8 Aksoy, I.A. (5) 38, 39 Akutagawa, S. (1) I08
Aladzheva, I.M. (1) 265 Alajarin, M. (7) 102; (8) 7, 49 Alamgir, M. (8) 265-267 Alazard, J.P. (7) 103 Albericio, F. (6) 63, 196 Alberti, M. (8) 184 Alcaraz, J.M. (1) 403 Aldenhoven, H. (1) 60, 61 Aleksandrova, I.P. (8) 141 Alewood, P.F. (4) 40;(5) 21-23 Alexakis, A. (4) 28 Al’fonsov, V.A. (5) 235 Alias, A. (7) 110; (8) 47, 54 Alings, C. (6) 147 Al-Juaid, S.S. (1) 179, 373 Alkins, E. (8) 231 Allan, R.D. (5) 228 Allcock, H.R. (8) 80, 101, 118, 133, 135, 136, 139, 148, 149, 160, 198, 211, 212, 217, 219, 227, 232, 233, 235, 240, 243, 246, 268, 29 1, 296 Allen, C.W.(8) 100, 134, 159 Al-Madfa, H.A. (8) 143, 146 Al-Resayes, S.I. (3) 33 Altman, S. (6) 228 Altmeyer, 0. (1) 341 A M , R.H. (6) 62 Aly, A.A.M. ( I ) 229 Amrna, J.P. (4) 27; (5) 18 Anand, B.N. (2) 28 Anasako, Y. (8) 178 Anderson, C.B. (3) 20 Anderson, D.W. (5) 212 Anderson, R.A. (1) 174 Anderson, R.C. (1) 157 Ando, D.J. (7) 62 Ando, H. (8) 162, 168, 170, 171 Andraki, M.E. (6) 134
360
Andre, F. (6) 323 Andrus, A. (6) 66 Ang, H.G.(1) 221; (8) 93, 94 Angelov, Ch.M. (5) 261 Annan, T.A. (1) 29 Anslyn, E. (6) 8 Antipin, M.Yu. (1) 265 Antipov, E.M. (8) 256, 258-260 Antonovich, V.A. (1) 28 Anuradha, K. (5) 13 Anzai, S. (8) 176 Apperley, D.C. (2) 29 Arbuckle, B.W. (1) 110 Arbuzov, B.A. (1) 139, 287-290, 299-303 Archarlis, A. (7) 35 Arif, A.M. (1) 368; (2) 21; (5) 241, 302, 305 Arjunan, P. (6) 270 Armstrong, R.W. (7) 21 Arndt, V. (1) 45, 50 Arora, S.K. (6) 270 Arques, A. (1) 151; (7) 106, 109, 110; (8) 15, 43, 47, 54, 55 Arshinov, R.P. (5) 290 Artschwager-Perl, U. (7) 41 Artyushin, 0.1.(1) 182 Asensio, G. (1) 66 Ashley, G.W. (6) 220 Ashton, P.R. (5) 266 Asseline, U. (4) 60; (6) 110, 190 Athey, P.S. (5) 8 4 Atkins, E.D.T. (8) 210 Atoh, M. ( I ) 73 Atta, S.M.S. (5) 284 Attanasi, O.A. (7) 38 Atwood, J.L. (1) 52, 53. 320 Auhert. T. (7) 113
Author Index Auclair, C. (6) 291 Aumelas, A. (7) 123 Aurup, H. (6) 238 Austin, P.E. (8) 291 Au-Yeung, B. W. (1) 25 Avall, A.-K.C. (5) 131 Avotins, V. (8) 249 Awad, W.I. (1) 144 Ayed, N. (5) 242 Azzouzi, F. (7) 55 Baba, M. (6) 21, 29 Baboulene, M. (5) 63, 97 Babudri, F. (4) 8 Baccar, B. (5) 242 Baccolini, G. (1) 393 Baceiredo, A. (1) 192-195; (3) 32; (5) 286; (8) 117, 197 Bach, C. (6) 297 Bachrach, S.M. (1) 286, 372 Badawey, E.S.A.M. (8) 95 Badia, M.C. (5) I15 Badri, M. (5) 65, 246, 248 Badrudin, S.P. (5) 215 Baer, D.R. (8) 104 Baguley, B.C. (6) 283, 285, 309 Bailey, P.L. (5) 154 Bain, J.D. (6) 97 Bains, R. (2) 28 Baird, W.M. (6) 295 Bajwa, J.S. (1) 157 Baker, A.D. (6) 31 I Baker, C.H. (6) 45 Baker, G.R. (5) 50 Baker, M.J. (4) 21 Baker, R. (5) 36, 41 Baker, S.R. (1) 172 Balaban, A.T. (5) 121 Balakrishna, M.S. (4) 24 Balch, A.L. (1) 171 Baldus, H.-P. (4) 81 Ballou, C.E. (5) 42 Balogh-Hergovich, E. (8) 25 Balueva, A.S. (1) 139 Balzarini, J . (6) 12, 18, 21 Bancroft, D.P. (6) 301 Banduryan, S.I. (8) 257 Bankmann, M. (1) 325; (3) 18 Banks, M.A. (1) 87 Bannikova, O.B. (5) 108 Bannworth, W.( 5 ) 25 Bano, M.C. (8) 235 Bansal, R.K. (1) 390 Banzon, J. (6) 45 Baran, (3.0.(1) 216; (4) 26 Baraniak, J . (5) 95 Barbarella, G. (6) 324
361 Barbato, S. (6) 182 Bardos, T.J. (6) 33 Barendt, J.M. (4) 30 Barion, D. (1) 308 Barker, A.J. (7) 81 Barluenga, J. (1) 66, 237, 253; (7) 22, 49, 50; (8) 2, 61, 62, 70 Barrans, J. (1) 206, 344, 397, 398; (4) 76; (8) 191, 192 Barsegyan, S.K.(1) 140 Barta, T.A. (5) 184 Bartel, D. (6) 241 Barth, A. (1) 266 Barton, D.H.R. (5) 153 Barton, J.K. (6) 278, 313 Barton, S.D. (2) 5 Bartsch, R. (1) 388; (8) 87 Barvau, J . (5) 135 Ba-Saif, S.A. (5) 72 Bashkin, J.K.(4) 53; (6) 168, 169, 246 Basil, J.D. (1) 10 Bassett, M. (1) 128 Bastiaans, H.M.M. (1) 337 Bastian, H. (1) 271 Basu, A. (6) 183, 184 Bateson, J.H. (7) 79 Bats, J.W. (1) 415; (8) 193 Batyeva, E.S. (5) 235 Baudin, G. (5) 139 Baudler, M. (1) 44-51, 384-387 Baudry, D. (1) 383 Bauer, S. (1) 9, 304, 305 Baumann, K. (5) 20 Baumeister, U. (5) 298 Baures, P.W. (1) 16 Bawalda, P.L. (8) 151 Bayandina, E.V. ( 5 ) 236 Bayer, K. (5)223 Baze, M.E. (6) 60 Beachley, O.T. (1) 87 Beak, P. (5) 277 Beaton, G. (4) 61; (6) 121, 125 Beaucage, S.L.(6) 101, 142 Beaucourt, J.-P. (7) 85 Beaudry, W.T. (5) 91, 288 Bebendorf, J. (1) 243 Beche, G. (7) 51 Becker, G. (1) 3 1, 333 Bedel, C. ( I ) 412; (7) 10; (8) 195 Begley, T.P. (6) 177 Beijer, B. (6) 91, 143, 144 Bekiaris, G. (1) 21 1 Bekker, A.R. (4) 37 Bel, P. (5) 218 Belakhov, V.V. (5) 260
Bellamy, F. (3) 4; (7) 17, 88 Bellan, J . (1) 391; (4) 74 Bendayan, A. (1) 109 Benigni, D.A. (1) 172 Benkovic, S.J. (6) 81 Benmaamouf-Khallaayoun, Z. (5) 97 Benn, R. (1) 335 Bennani, Y.L. (5) 126, 207 Benner, S.A. (6) 133 Bennet, J.L. (8) 160 Bennett, M. (7) 117 Benseler, F. (6) 238 Bent, E.G. (4) 29 Bentrude, W.G. (2) 21; (5) 304, 305 Berchadsky, Y. (1) 12; (5) 215 Bergman, R.C. (1) 174 Bergstrasser, U. (1) 204 Berkin, D.M. (1) 376 Berlin, K.D. (5) 13 Berlin, W.K. (4) 43; (5) 29 Bermel, W. (6) 257 Bernadou, J. (6) 293 Bernaets, R. (6) 22 Bernal, 1. (5) 70 Bernotas, R.C. (1) 156 Berry, D.E. (6) 294 Bertrand, G. (1) 192-195; (3) 32; ( 5 ) 286; (8) 117, 197 Besnier, I. (5) 206 Bespal’ko, G.K. (2) 31; (8) 77 Bessho, K. (4) 10 Bestmann, H.J. (7) 15, 75 Betz, P. (1) 88, 335 Beveridge, D.L. (6) 260 Bevierre, M.-0. (1) 378 Bezoari, M.D. (8) 181 Bhalerao, U.T. ( I ) 189; (3) 9; (5) 85 Bhan, P. (6) 130 Bharadwaj, P.K. (1) 110 Bi, B.T. (7) 55 Bickelhaupt, F. (1) 337, 414 Biede-Charreton, C. (6) 292 Biedenbach, B. (1) 335 Bieher, K. (1) 402 Bielawska, H.(5) 104 Bildstein, B. (5) 237 Biller, S.A. (5) 115, 116, 186; (7) 54 Billington, D.C. ( 5 ) 36, 50 Bina, M. (6) 80 Binger, P. (1) 204, 334-336 Bin Shawkataly, 0. (1) 24 Bird, C.W. (1) 375; (8) 186 Birdsall, W.J. (8) 80 Birkel, M. (1) 331
362 Birrell, G.B. (6) 333 Birse, E.F. (3) 21 Bischofberger, N. (6) 74, 192 Bischoff, P. (6) 17 Bishop, J.M. (6) 117 Bissinger, P. (1) 81 Bitterer, F. (1) 208 Biyushkin, V.N. (5) 301 Bjergarde, K. (6) 73 Blachnik, R. (4) 81 Blackburn, G.M. (5) 266; (6) 53-55 Blakley, T.J. (8) 236 Blinn, D.A. (1) 100 Bloch, G. (6) 323 Bloch, W. (6) 79 Blbcker, H. (6) 147 Blommers, M.J.J. (6) 215 Blum, H. (5) 151, 214 Blum, J . (8) 65 Blum, 0. (1) 178 Boal, J. (6) 111 Bobst, A.M. (6) 199, 200 Boche, G. (5)276 Bochkov, V.N. (5) 32 Bock, H. (1) 274, 325; (3) 18 Bodalski, R. (4) 5; (5) 76, 77, 134 Bodepudi, V. (6) 68 Boder, N. (5) 5 Boeckman, R.K. (5) 184 Bbgge, H. (1) 135, 271, 272, 306, 416, 420 Boese, R. (1) 269, 374 Boganova, N.V. (4) 15; (5) 213 Boger, D.L. (6) 80, 271, 272 Bogusiak, J . (5) 49 Bohle, D.S. (1) 218, 351; (7) 31 Boiko, L.D. (8) 76 Boisdon, M . T . (1) 206, 344; (4) 76 Boldeskul, I.E. (1) 291 Bolelaya, N.K. (8) 76 Bolen, J.B. (5) 166 Bollens, E. (8) 37 Bollinger, J.M. (6) 45 Bolton, P.H.(6) 247 Bondarenko, N.A. (1) 129; (5) 143 Bonfils, E. (6) 201 Bongini, A. (7) 38 Bonnet, J.P. (8) 124 Bookham, J.L. (1) 95 Books, J.T. (8) 241 Bordieu, C. (1) 359, 409 Borisenko, A.A. (1) 68, 69, 280 Borisenko, V.P. (8) 97 Borisenkova, E.K.(8) 253, 258,
Organophosphorus Chemistry 259 Boritzki, T.J. (6) 283 Bornancini, E.R.N. (1) 63 Bortolus, P. (8) 105 Bose, N.K.(6) 64 Bose, R.N. (6) 306 Bosio, L. (8) 210, 231 Bosold, F. (5) 276 Bosyakov, Yu.G. (1) 102, 103 Bott, S.G. (1) 52, 53, 320 Boubia, B. (7) 17 Boukbir, L. (8) 224 Boulos, L.S. (7) 25, 26, 28 Bourdieu, C. (5)269 Bovermann, G. (5) 223 Bovin, A.N. (5) 295, 296 Bowmaker, G.A. (8) 16 Bowmer, T.N. (8) 261 Brandi, A. (3) 31 Brandsma, L. (1) 21 Brandt, K. (8) 112, 121, 129, 142 Brauer, D.J. (1) 208 Braun, R. (4) 80; (5) 231-233 Bravo, J. (8) 270, 271 Breiner, R.G. (6) 33 Breker, J. (1) 198; (5) 240 Brel’, V.K. (5) 256, 259 Bremer, M. (7) 15 Brennan, D.J. (8) 148 Brenton, A.G. (6) 327 Breslow, R. (6) 8 Breuer, E. (5) 176, 218, 273, 274 Brianese, N. (1) 59 Bridges, A. (8) 159 Brieden, W. (1) 18 Briki, F. (6) 332 Brill, W.K.-D. (4) 61; (6) 120, 121 Bringewski, F. (1) 114 Broder, S. (6) 112, 113 Brodtbehrer, P.R. (6) 27 Broeders, N.L.H.L. (6) 38 Bronson, J.J. (6) 27 Brovarets, V.S. (1) 260 Brown, D.E. (8) 134 Brown, J.M. (3) 3 Brown, M.L. (5) 302 Brown, P.S. (3) 19 Broxterman, H.J.G. (4) 45 Bruce, M.I. (1) 24 Bruche, L. (7) 104; (8) 57 Bruggink, A . ( 5 ) 79, 80 Bruins Slot, H.H. (5)80 Brunner, H. (1) 4, 14, 117; (4) 65 Brush, C.K. (6) 318
Bruzik, K.S.(6) 37 Bryce, M.R. (7) 62, 63 Buchko, G.W. (6) 167 Buck, H.M.(6) 4, 38, 226 Buckley, L. (6) 248 Budde, K. (8) 179 Budzelaar, P.H.M. (1) 22 Buechler, G. (7) 121 Buescher, R. (8) 283 Bujacz, G. (1) 227 Bull, E.O.J. (5) 12, 59 Bundel, Yu.D. (1) 150 Buono, G. (2) 25; (7) 35 Burangulova, R.N. (5) 17 Burdsall, D.C. (5) 130 Burford, N. (1) 364; (4) 72 Burgada, R. (5)297 Burgess, H . (4) 16 Burin, S.V. (8) 218 Burk, M.J. (1) 74, 75, 136 Burke, T . R . (5) 166 Burlini, N. (7) 59 Burmistrov, S.Y.(4) 38 Burnaeva, L.A. (2) 13; (5) 17 Burns, J.A. (1) 125 Burton, D.J. (5) 163; (7) 71 Burton, S.D. (2) 1 Busch, T. (1) 317, 340, 341 Bushnell, G.W. (1) 381 Busson, R. (6) 18 Butler, J.C. (1) 125 Button, R.S. (1) 100 Buttrey, L.A. (1) 87 Buzykin, B.I. (5) 264 Byistro, V.K. (1) 280 Cabal, M.P. (7) 118 Cadet, J. (6) 335 Cadogan, J.I.G. (4) 9; (5) 195, 196 Caesar, J.C. (7) 9 Cai, B. (1) 395, 396; (2) 34 Cai, M. (5) 106 Cai, X.M. (8) 93, 94 Cairns, M.S. (1) 249 Calabrese, J.C. (1) 136 Camaioni, N. (8) 105 Cambon, A. (8) 37 Camellini, M . T . (7) 31 Cameron, T.S.(8) 20 Caminade, A.-M. (1) 170, 349; (5) 65, 246-248 Camp, D. (1) 106; (3) 12 Campbell, A S . (5) 164 Campbell, M.M. (5) 174, 212; (7) 81 Campos, P.J. (1) 66
363
Author Index Canal, G. (1) 66 Candle, L.J. (3) 35 Cano, F.H. (8) 7 Cao, J.-H. (5) 141 Caoley, A.H. (5) 241 Caperelli, C.A. (6) 5 Capobianco, M.L. (6) 324 Capuano, L. (7) 36 Carbonnaux, C. (6) 326 Carey, J.V. (3) 3 Carite, C. (7) 103 Carrnichael, D . (1) 373, 401 Carr, S . (6) 294 Carreira, E.M. (7) 95 Carrera, G.M., jun. (7) 19 Carrick, C. (5) 41 Carrie, R. (1) 297 Carroll, S.S. (6) 81 Cartagena, I. (1) 151; (7) 106 Cart& B.K. (6) 294 Carter, B.J. (6) 249, 251-253 Caruthers, M.H. (4) 61; (6) 120, 121, 125 Casas, C. (6) 290 Casida, J.E. (5) 89, 90 Castagnino, E. (5) 153 Castedo, L. (3) 24, 25 Castellato, U. (1) 59; (3) 36 Castro-Pichel, J . (6) 34 Catalan, J . (8) 7 Cates, L.A. (5) 96 Cavell, R.G. (1) 247; (2) 32, 33; (8) 69, 84, 199 Cech, D . (6) 187 Cech, T.R. (6) 227, 239 Cedergren, R. (6) 237 Cereghetti, M. (1) 107 Cerny, J . (6) 23 Ceruzzi, M. (6) 119 Cetrullo, J . (5) 70 Cevasco, G. (5) 270 Chacon, S.T. (1) 24 Chadha, M.S. (1) 163 Chai, W. (5) 289 Chamberlin, A.R. (6) 97 Chan, S. (1) 109 Chandrasekhar, T.K. (8) 155 Chandrasekhar, V. (8) 155 Chang, J.Y.(8) 136 Chang, S.C. (8) 289 Chao, Z.J. (8) 224 Charubala, R. (6) 107, 137, 138 Chatterjee, M. (6) 191 Chatterton, P.M. (8) 250 Chattopadhyaya, J . (6) 244, 245 Chekhlov, A . N . (3) 14; (5) 188, 295, 296, 303 Chen, C. (7) 29
Chen, H. (1) 25 Chen, J . (5) 157; (6) 222 Chen, J.-D. (1) 13 Chen, R. (1) 395, 396; (2) 34; (5) 67, 210 Chen, W . (5) 47, 58, 8 Chenault, J . (1) 256 Cheney, D.L. (5) 78 Cheng, L.-T. (1) 126 Cheng, M.-C. (1) 83 Cheng, S.J. (8) 130 Cheng, T. (5) 106 Cheng, Y.C. (6) 114 Chen-Yang, Y . W . (8) 130, 132 Cheong, C. (6) 217 Cherches, G.Kh. (8) 119 Cherkasov, R.A. (2) 12; (5) 98, 100, 187, 202, 257, 258; (8) 38, 39 Chernega, A . N . (1) 346, 347; (4) 67-69; (8) 30 Chernov, P.P. (2) 8, 15 Chertanova, L.F. (1) 301 Chetcuti, P. (6) 279 Chichester-Hicks, S . V . (8) 254, 26 1 Chikashita, H. (6) 265 Chin, D.J. (6) 118 Chin, J . (6) 39 Chiorri, C. (5) 119 Chiquete, L.M. (2) 23 Chistokletov, V . N . (1) 181; (5) 17, 158, 159 Chivers, T. (8) 187 Chmielewski, J . (6) 219 Cho, W.J. (8) 214 Cho, Y. (4) 62; (6) 123 Choi, W . S . (5) 105 Chojnowski, J . ( I ) 200 Chordia, M . D . (7) 115 Chorev, M. (5) 176, 218, 274 Chou, W.-N. (3) 15; (7) 5; (8) 14 Choukroun, R. ( I ) 349 Chow, F.L. ( I ) 25 Chow, M. (8) 235 Christensen, J.W. (7) 18 Christner, D.F. (6) 258, 259 Chu, B.C.F. (6) 307 Chu, C.K. (6) 50 Chudakova, T.I. (5) 93 Chugunov, Y . V . (4) 11 Chukova, V.M. (8) 226 Chumakov, Yu.M. (5) 301 Chung, K.H. (1) 146 Chunming, Z. (7) 44 Churchill, M.R. (1) 87 Chuvashev, D . D . (1) 220
Cicchi, S. (3) 31 Ciosek, C.P. (5) 115, 186 Cirolo, M.R. (6) 250 Clararnunt, R.M. (8) 7 Clardy, J . (6) 263, 265 Clare, M. (7) 89 Clark, G.R. (1) 218 Classon, B. (1) 215 Clore, G.M. (6) 195 Cobb, J.E. (5) 28 Coe, D . M . (6) 49 Coe, P.L. (6) 12 Coggio, W . D . (8) 149 Cohen, J.S. (6) 106, 112, 113 Cohen, S. (8) 235 Cole-Hamilton, D.J. (1) 20 Coleman, R.S. (6) 176; (7) 118 Coley, S . M . (8) 198 Collet, A. (6) 194 Collier, D . A . (6) 209, 214 Collignon, N . (5) 127, 133, 225 Collin, J. (3) 10 Coltrain, B.K. (8) 284 Comber, M.F. (1) 225 Conary, G.S. (3) 35 Conda, L. (8) 158 Connolly, B.A. (6) 173-175 Contreras, R. (2) 23 Coogan, M.P. ( I ) 361; (5) 271 Corcoran, R.C. (5) 205 Cordi, A . A . (5) 119 Corey, E.J. (7) 47 Cormier, J.F. (6) 86 Corsano, S. (5) 153 Cosquer, P. (1) 297 Cosstick, R. (6) 161, 173-175 Costisella, B. (5) 124, 149 Cotton, F . A . (1) 13 Couladouros, E. (7) 119 Coull, J.M. (6) 189 Courbis, P. (4) 64 Courtois, G. (5) 194 Cowan, J . A . (6) 314, 315 Cowley, A.H. (1) 27, 52-54, 57, 200, 268, 276, 320, 354, 368 Cox, M.B. (6) 270 Craig, D.C. (1) 23; (5) 287 Cramer, C.J. (2) 3 Cregge, R.J. (7) 82 Crilley, M.M.L. (4) 3; (5) 120 Cristau, H.-J. ( 1 ) 116, 259; (3) 1; (7) 48; (8) 66, 67, 83 Cromrnen, J . (8) 234, 292 Crosby, K.M. (8) 269 Cross, S. (6) 290, 291 Cube, R.V. (1) 156 Culcasi, M. (1) 12 Cullen, W.R. (1) 24
364 Cummins, L. (6) 125 Cunningham, R.P. (6) 247 Cupertino, D.C. (1) 20 Curtin, M.L. (3) 28 Curtis, R.D. (1) 350; (8) 13 Cushman, C.D. (6) 130 Cypryk, M. (1) 209 Dabbagh, H.A. (1) 147 D’achenko, M.V. (8) 230 Dagle, J.M. (6) 134 Dahan, F. (1) 177 Dahl, B.H.(6) 73 Dahl, 0. (6) 73 Dahn, S.C. (6) 230 Dajaegree, A. (6) 330 Dake, L.S. (8) 104 Dalpozzo, R. (1) 393 Damerius, R. (8) 120 Damha, M.J. (6) 61, 141 Dan, S. (5) 210 Dange, V. (6) 252 D’Angelo, L.L. (6) 325 Daniel, L.W. (6) 14 Daniels, L.M. (4) 27; (5) 18 Danishefsky, S.J. (7) 118 Dannoue, Y. (6) 254 Danoff, S.K.(5) 34 Danopoulos, A.A. (1) 82 D’Anrea, S.V. (4) 14 Danzin, C. (6) 32 Dappen, M.S. (5) 119 Dargatz, M. (1) 32; (5) 298 D’Ari, R. (6) 185 Dartiguenave, M. (1) 232; (3) 32; (8) 36, 117 Dartiguenave, Y. (1) 232; (3) 32; (8) 36, 117 Dartmann, M. (1) 307 Darzynkiewicz, E. (6) 11 Das, S.K.(4) 27 Date, M. ( 5 ) 69 Daumas, M. (5) 198 Davidson, F. (1) 136 Davies, D.L. (1) 128 Davis, B.H. (1) 147 Davis, C.E. (8) 4 Davis, J.M. (5) 267 Davis, R.V. (4) 27; ( 5 ) 18 Davy, R.D. (8) 103 Day, R.O.(2) 1, 5, 6, 18, 20 Day, S . K . (5) 18 De, B. (7) 47 Debouzy, J.-C. (6) 13 Debrosse, C. (6) 294 DeCanio, E.C. (1) 13 De Clercq, E. (6) 12, 18, 21,
Organophosphorus Chemistry 24, 29, 30 Declercq, J.-P. (1) 284 Degenhardt, C.R. (5) 130 Dehmlow, E. (1) 264; (8) 18 Dehnicke, K. (8) 294 DeHoniesto, J. (5) 219 DeJaeger, R. (8) 206 De Kanter, F.J.J. (1) 414 Dekura, T. (8) 185 Delange, B. (5) 115 de Leon, E. (3) 6; (4) 6 Dellinger, D. (6) 125 Delmas, M. (5) 246 Delorme, D. (5) 126 de 10s Santos, C. (6) 184 Demassier, V. (6) 323 Dembek, A.A. (7) 61; (8) 135, 160 Dembowski, U. (1) 58 Denis, J.M. (1) 115, 324, 326; (5) 113 Denmark, S.E. (3) 27; (5) 250; (7) 52, 69 Dennis, T.J. (1) 323 Denny, W.A. (6) 279, 283-285, 309 dePaz, J.L.G. (8) 7 Depazay, J.C. (7) 84 De Ruiter, B. (8) 150 Dervan, P.B. (6) 212, 213 DeSolms, S.J. ( 5 ) 36 Desorcie, J.L. (8) 101, 159, 217 Despax, C. (4) 12; (5) 9, 48 Deutsch, T.F. (6) 248 Devaud, M. (7) 55 Devenyi, J. (7) 76 De Vine, R.J. (6) 134 Devine, R.L.S. (8) 135 De Voss, J.J. (6) 267 de Vroom, E. (6) 251 Dhawan, B. (5) 68, 203 Diallo, O.S. (1) 397, 398; (8) 191, 192 Dieck, H. (5) 263 Diefenback, U. (8) 120 Diel, P.J. ( 5 ) 191, 220 Diemert, K. (1) 86, 219, 362; (4) 78 Dillon, K.B. (2) 7 Dimmig, T. (5) 52 Ding, L. (6) 289-291 Ding, W.-D. (6) 267 Dipchand, A.I. (1) 364; (4) 72 Ditrich, K. (7) 93 Dixon, H.B.F. (5) 175, 183 Dixon, R.M. (6) 57 Dmitrichenko, M.Yu. (5) 109, 110; (8) 40, 196
Dmitriev, V.I. (1) 92 Dodge, J.A. (1) 153; (8) 101 Dorges, C. (1) 406-408 Doernhoefer, C. (8) 147 Doerrenbach, F. (1) 208 Doi, J.T. (1) 110 Dolgushin, G.V. (5) 110; (8) 40, 196 Dolgushina, T.S. (5) 245 Dolitzky, B.-Z. (5) 193 Dollase, W.A. (5) 214 Dominey, L.A. (8) 236 Donaghy, K.J. (1) 298 Dong, H. (6) 322 Donnely, J.A. (4) 16 Donskikh, V.I. (1) 220; (5) 110; (8) 40, 196 Dorbath, B . (1) 198 Dorow, R.L. (5) 250; (7) 69 Dostal, K. (8) 184 Dou, D. (1) 167 Douce, L. (1) 26 Doudna, J.A. (6) 240 Douglas, M.E. (6) 161 Doxsee, K.M. (1) 138 Doyle, T.W. (6) 260 Drach, B . S . (1) 260 Drapailo, A.B. (4) 69 Draper, K. (6) 119 Dreef, C.E. (5) 138; (6) 104 Dreef-Tromp, C.M. (6) 104, 193 Drescher, S . (7) 36 Driscoll, J.A. (1) 166 Drysdale, M.J. (7) 46 Dubourg, A. (1) 284 Duchamp, J.C. (1) 276 Duesler, E.N.(1) 167; (3) 35 Duster, D. (1) 387 Dufour, N. (1) 349 Duh, J.-L. (6) 199, 200 Dukescherer, D.R. (5) 221 Dumas, J. (7) 84 du Mont, W.-W. (1) 210 Dunaway-Mariano, D. (5)230 Dunn, B. (8) 148 Dunn, D.A. (6) 248 Dunn, J.A. (6) 33 Duplantier, A.J. (7) 92 Dupreez, J.G.H. (3) 36 Durand, T. (7)83 Durrant, I. (4) 48; (6) 198 Dutkiewicz, J. (8) 141 Dvonkin, A.A. (8) 298 Dvorakova, H. (6) 26 Dybkowski, P. (5) 156 Eaborn, C. (1) 179
Author Index Ealick, S. (5) 304 Ebel, J.P. (6) 223 Ebetino, F.H. (5) 130 Ecka, H.-L. (4) 7; (5) 125 Eckstein, F. (6) 5 1, 238 Edwards, M.L. (3) 5; (7) 60 Edwards, P.G. ( I ) 82 Efremov, D.A. (5) 62 Efremov, Yu.Ya. (1) 290, 299, 300; (5) 257
Egan, W. (6) 101, 111 Eggleston, D.S. (1) 16 Eguchi, S . (4) 13 Ehle, M. (1) 331 Ehresmann, B. (6) 223 Ehresmann, C. (6) 223 Ehrhard, A. (6) 32 Ehrig, M. (1) 295 Eickhoff, W.M. (8) 274 Einhorn, C. (I) 149 Einhorn, J. (1) 149 Einstein, F.W.B. (1) 24 Eisenberg, M. (6) 183 Eisenhaber, F. (6) 277 El-Batouti, M. (1) 251, 252 Elbaum, B. (8) 127 Eleftheriou, M.-E. (5) 285 El Essawi, M. (1) 244 El-Farargy, A.F. (5) 283 Elgamal, S . (8) 65 Elguero, J. (8) 7, 15 Elhaddadi, M. (5) 216, 217 Eliel, E.L. (5) 73 Elkatab, A.A. (7) 28 El Khalik, S.A. (1) 244 El-Khoshnieh, Y.O. (5) 284; (7) 25
Ella, C.J.J. (5) 138 Ellestad, G.A. (6) 267 Ellington, A.D. (6) 243, 299 Ellis, G. (8) 251 Ellman, J.A. (6) 95, 96 El Manouni, D. (5) 297 Elnaem, S.I. (7) 28 Elschenbroich, C. (1) 402 Elsevier, C.J. (8) 92, 200, 201 Elvahman, N.M.A. (7) 26 Embrey, K.J. (6) 274 Enchev, D.D. (5) 261 Endo, T. (6) 131 Engel, R. (1) 223, 224 Engelhardt, U . (8) 120 Engels, J.W. (4) 63; (6) 129, 145
English, U. (6) 100 Enjalbert, R. (8) 122, 124, 125 Ennis, M.D. (6) 60 Ephretikhine, M. (1) 383
365 Epishina, T.A. (5) 8 Erabi, T. (1) 255 Eritja, R. (6) 63, 166, 196 Erker, G . (7) 41 Erofeeva, M.R. (5) 158 Escale, R. (7) 83 Escarcella, M. (6) 196 Eschenmoser, A. (5) 20 Esipenko, A.N. (5) 53 Esker, J. (4) 42; (5) 19 Espenbetov, A.A. (1) 102 Essigmann, J. (6) 183, 184 Estevez, V.A. (5) 35 Etemad-Moghadam, G. (1) 284; (6) 289-291
Ethridge, V. (5) 305 Etzbach, T. (1) 384, 385 Evans, D.A. (7) 95 Evans, M.R. (4) 48; (6) 198 Evans, S.A. ( I ) 158 Exarhos, G.J. (8) 248, 269 Fackler, J.P. (1) 10 Fahmy, A.F. (5) 283; (8) 68 Falck, J.R. (7) 86 Falgueyret, J.-P.(7) 87 Falzone, C.J. (6) 322 Famulok, M. (5) 276 Fan, S. (8) 132 Fang, G. (7) 107 Farazi, V. (1) 100 Farina, V. (1) 172 Farnier, M. (7) 113 Farrell, N. (6) 308 Farschtschi, N. (4) 62; (6) 124 Fatou, J.G. (8) 251, 254, 261 Faucette, L.F. (1) 16 Fauq, A.H. (5) 38, 39 Fawcett, J. (3) 34 Fazakerley, G.V. (6) 326 Feaster, J.E. (1) 74 Feigon, J . (6) 319 Feng, K. (1) 392 Feng, R. (1) 76 Ferentz, A.E. (6) 160 Ferguson, G. (1) 254; (7) 12 Feringa, B.L. (1) 77 Fernandez-Forner, D. (6) 63, 166
Ferrar, W.T. (8) 284 Ferrara, L.M. (6) 27 Ferrero, M. (7) 49; (8) 61, 70 Ferris, C.D. (5) 34 Ferris, K.F. (8) 11, 12, 104, 247
Ferrond, D. (5) 206 Feshchenko, N.G. (2) 30
Fetisov, V.I. (5) 46 Fettinger, J.C. (1) 87 Feucht, G. (1) 37 Fewell, L.L. (8) 244 Fiandenese, V. (4) 8 Fife, T.H. (5) 71 Filali, A. (2) 27 Filbrich, R. (6) 206 Fild, M. (1) 113, 114 Filippone, P. (7) 38 Finnegan, P.M. (7) 89 Firth, S. (1) 323 Fitzpatrick, R.J. (8) 240, 243 Flamigni, L. (8) 105, 286 Fleischer, U. (1) 328; (4) 79 Flem, G.L. (8) 224 Floruss, A. (1) 51 Fluck, E. (1) 416-420; (4) 80; (5) 231-233; (8) 194
Foces-Foces, M.C. (8) 7, 54 Fokin, E.A. (5) 303 Fontanella, J.J. (8) 266 Ford, R.R. (8) 208 Foresti, E. (7) 38 Foricher, J. (1) 107 Forster, C. (5) 116, 186; (7) 54 Fortuniak, W. (1) 209 FOSS,V.L. (1) 68, 69, 280 Foster, A.L. (5) 144; (7) 68 Fotiadu, F. (7) 35 Foucaud, A. ( I ) 409, 410, 412; (5) 243; (7) 10; (8) 195 Fouquey, C. (5) 11 Francke, R. (1) 142 Francklyn, C. (6) 83, 300 Francois, P. (6) 152 Frank, B.L. (6) 258, 259 Frank, R. (6) 147 Franz, J.E. (5) 221 Franzus, B. (1) 147 Frebel, M. (1) 272 Freedman, J. (1) 155 Freeman, J.P. (4) 14 Freeman, S. (5) 182, 265 Freidzon, Ya.S. (8) 230 Freman, F. (6) 25 Frenking, G. (7) 51 Frenzel, M. (1) 377 Frick, W. (7) 73 Friedrich, C. (8) 210, 231 Friedrich, D.M. (8) 104 Frighetto, R.T.S. (7) 75 Frijns, J.H.G. (1) 22 Fritz, G. (1) 34-43, 203 Fritz, M. (1) 266, 322 Frolow, F. (1) 178 Froneman, M. (5) 14, 78 Froyen, P. (8) 45
366 Frerystein, N.A. (6) 316 Frye, J. (1) 199 Fujikawa, K. (6) 303 Fujimori, S. (6) 140 Fujimoto, T . (5) 33 Fujita, J . ( I ) 73 Fujiwara, H. (8) 154, 228 Fujiwara, M. ( I ) 255 Fukuda, N . (1) 17 Fukuda, R. (6) 281 Fulde, M . (1) 415; (8) 193 Fulop, V . (1) 400; (3) 13 Funaki, K. (8) 173 Furukawa, K. (6) 328 Furukawa, S . (5) 69 Furusawa, 0. ( I ) 263 Furuta, T. (7) 67 Furuya, S . (6) 266 Gabler, D. (8) 127, 128 Gaedcke, A . (5) 292 Gaffney, B.L. (6) 211 Gait, M.J. (4) 48; (6) 198, 234 Gajda, T. (5) 161, 162 Galishev, V . A . (5) 245 Gallazzi, M . C . (8) 161 Galy, J. (8) 122, 124, 125 Ganapathiappan, S. (8) 208 Gani, D. (5) 50 Gao, W.-Y. (6) 114 Gao, X. (6) 162 Gao, Z. (5) 140 Garanti, L. (7) 104; (8) 57 Garbers, H . V . (5) 86 Garcia, C. (8) 66 Garcia, R.G. (6) 144 Garcfa-Lbpez, T. (6) 34 Gard, G.L. (5) 150 Gard, J.K. (4) 53; (6) 168, 246 Garland, R.B. (7) 89 Garner, C . D . (5) 234 Gaset, A. (5) 246 Gasparutto, D. (4) 59; (6) 84 Gasparyan, G.Ts. ( I ) 140 Gastel, F. ( 5 ) 216 Gaudemer, A. (6) 292 Gaur, R.K. (6) 188 Gauss, D . H . (6) 100 Gazaliev, A.M. (5) 299 Gazizov, T.K. (4) 1 1 Ge, L. (6) 296 Geiser, T . (6) 108, 109 Genest, D. (6) 332 Genet, J.P. ( I ) 118; (4) 4, 36; (5) 206 Gentles, R.G. (6) 156 Geova, L.V.(8) 188
Organophosphorus Chemistry Geribaldi, S. (7) 66 Gerlach, B. (4) 44; (5) 27 Gerlt, J.A. (6) 247 Getman, K.M. (5) 221 Gheorghui, M . D . (5) 121 Ghosh, A . (4) 14 Ghosh, S.K. (1) 163 Giannaris, P.A. (6) 61, 141 Gibson, B.W. (6) 6 Gibson, D. (5) 176, 274 Gieske, T . H . (7) 82 Gigon, A. (7) 85 Gildea, B.D. (6) 189 Gill, G.B. (7) 117 Gillette, G.R. (1) 192, 193 Gillier, H . (5) 297 Gilyarov, V . A . (8) 78 Giralt, E. (6) 63, 196 Girard, G.R. (I) 16 Girard, J.-P. (7) 83 Givens, R.S. (5) 84 Glaser, R. (2) 4 Glegg, W . (5) 234 Glenmarec, C. (6) 244, 245 Gleria, M. (8) 105, 161, 286 Glowacki, Z. (5) 170 Gmeiner, W.H. (6) 170 Goesmann, H. (1) 43 Gohsh, D . (6) 327 Gold, L. (6) 298 Goldberg, I.H.(6) 258, 259 Gol’dfarb, E.I. (2) 14, IS Golding, B.T. (4) 3; (5) 120 Goldschmidt, B. (5) 26 Golina, S.I. (8) 225, 226 Golinski, M. (7) 91 Golokhov, D.B. (4) 20 Gololobov, Y.G. (5)45 Golova, L.K. (8) 255-257, 273 Gornez, M.A. (8) 251, 254, 261 Gonbeau, D . ( I ) 285 Gonce, F. ( I ) 170; (5)247 Gong, B. (5) 81 Gordillo, B. (5) 73 Gordon, E.M. (5) 115, 186 Gorenstein, D.G. (4) 62; (6) 123, 124, 320 Goreva, T . V . (5) 8 Gorgues, A. (5) 65; (7) 64, 65 Gosink, H.J. (8) 204 Gosovami, B. (6) 164 Goti, A . (3) 31 Gott, J.M. (6) 172 Gottikh, M. (6) 190 Goubitz, K. (8) 200 Goudetsidis, S. (5) 151 Gougoutas, J.Z. (7) 53 Gourdie, T.A. (6) 283, 284
Gouyette, C. (6) 13 Gouygou, M. ( I ) 284, 285 Graber, P. (6) 195 Grachev, M.K. (4) 37, 38 Graczyk, P. (1) 227 Grblund, A . (6) 312 Graff, D. (6) 125 Grajkowski, A . (6) 37 Grandas, A . (4) 61 Grandos, A. (6) 121 Granger, J.N. (4) 62; (6) 123 Granier, M. (1) 194, 195; (3) 32; (5) 286; (8) 117, 197 Graulich, J . (1) 402 Gravatt, G.L. (6) 283, 285 Gravier-Pelletier, C . (7) 84 Graziani, R. (1) 59; (3) 36 Grew, M . N . (5) 121 Gree, R. (7) 85 Green, G.A. (6) 118 Green, J.M. (5) 205 Green, R. (6) 241, 243 Greenbaum, S.G. (8) 266 Greeves, N. (3) 19 Griffith, O . H . (5) 137; (6) 333 Griffiths, D . V . (7) 9 Griffiths, P.A. (7) 9 Grigoryan, N.Yu. (1) 235 Grimaldo-Moron, J.T. (1) 228; (3) 11 Grobe, J. ( I ) 101, 307, 327 Gronchi, G. ( I ) 12 Gronenborn, A . M . (6) 195 Gross, H . (5) 122, 124, 149 Grubb, R.H. (7) 32 Griitzmacher, H . (1) 242, 296, 328, 343; (4) 79; (5) 239; (7) 14; (8) 32 Grunberg-Manago, M. (6) 223 Grushin, V . V . (1) 175 Gu, Q. (5) 106 Gubnitskaya, E.S. (5) 226 Gudat, D. (1) 339; (4) I; (8) 5 Gudima, A . (1) 281; (4) 73; (8) 205, 298 Gudrun, U . ( I ) 31 Gueck, J . (5) 20 Guenot, P. (1) 326 Guerk, G. (8) 113 Gughaev, A . V . (5) 62 Gug-Kim, S . (4) 54, 55; (6) 70 Guilard, R. (7) 113 Guillemin, J.C. ( I ) 115, 324, 326; (5) 113 Gumus, F. (6) 15 Guo, F. (8) 44 Guo, M. (7) 77 GUO,M . 4 . (5) 266; (6) 53-55
367
Author Index Gupta, A. (1) 390 Gupta, K.C. (6) 64,202 Guranowski, A. (5) 266; (6) 5 4 Gusar, N.I. (7) 100 Gusarova, N.K. (1) 92, 93, 159 Guy, A. (6) 151 Gvozdetskii, A.N. (2) 26 Gyor, M. (1) 190 Ha, T.-K. (1) 363 Haas, J. (1) 336 Habhadi, N. (1) 232 Haber, S. (1) 374 Habliston, D.L. (6) 333 Hacker, M.P. (6) 308 Haddon, R.C. (8) 251, 254, 261 Hadjiarapoglou, L. (5) 16 Hadzic, P.A. ( 5 ) 293 Haegele, G. (5) 151, 214, 292 Haenel, M.W. (1) 88 Hanssgen, D. ( I ) 60, 61 Hafez, T.S. (5) 283, 284 Hagiwara, S. (4) 13 Hahn, J. (1) 44 Hahn, M. (1) 386 Hahn, T. (1) 86 Halazy, S. (6) 33 Haller, F. (7) 51 Haller, S. (8) 36 Haltiwanger, R.C. (4) 29, 30 Hamad, M.M. (5) 283 Hamada, Y. (5) 300 Hamanaka, N. (1) 222 Hamano, M. (6) 275 Hambley, T.W. (3) 26; (5) 228 Hammerschmidt, F. (5) 171-173, 223, 224 Hammond, P.S. ( 5 ) 268 Hampp, A. (1) 71 Han, F.S. (6) 114 Handel. H. (2) 27 Handlon, A.L. (6) 5 8 Hanessian, S. (5) 126, 207 Hani, R. (8) 4 Hanke, D. (1) 43 Hanker, I. (6) 52 Hanna, M. (6) 241 Hanna, M.T. (1) 251, 252 Hanrahan, J.R. (5) 228 Hanson, A.K. (8) 11 Hanson, B.E. (1) 89 Harada, K. (6) 135 Harangi, J. ( 5 ) 293 Harayama, T. (4) 10 Hardee, J.R. (1) 199 Harger, M.J.P. (1) 361; (5) 265, 271, 275
Harlow, R.L. (1) 74, 75, 136 Harms, K. (7) 51 Harris, C.M. (6) 157, 318 Harris, F.M. (6) 327 Harris, P.A. (6) 181 Harris, P.R. (1) 54 Harris, R.K. (2) 29 Harris, T.M. (6) 157, 318 Harrison, K.N. (4)21 Harrity, T.W. (5) 115, 186 Hartung, H. (5) 298 Hartwig, J.F. (1) 174 Harusawa, S. (5) 107; (8) 56 Harvey, R.G.(6) 155 Hasegawa, Y. (5) 94 Haseltine, J.N. (7) 118 Hasenbach, J. (1) 51 Hashimoto, K. (8) 285 Hashimoto, M. (8) 99 Hashimoto, S. (1) 382; (8) 74, 75 Hasimoto, Y. (6) 140 Hassaneen, H.M. (8) 6 8 Hassanein, M. (1) 245 Hasselbring, R. (8) 33 Hassler, K. (1) 33 Hata, T. (4) 56-58; (5) 60;(6) 71, 72, 122 Hatano, K. (5) 300 Hau, J.F. (4) 60;(6) 110 Hauck, S.I. ( I ) 172 Haug, W. (1) 294, 317 Haught, J. (6) 80 Haupt, E.T.K. (5) 263 Hausel, R. (1) 134 Hausheer, F.H. (6) 128 Havelka, K.O. (7) 61 Haw, J.F. (8) 107, 108, 127, 128 Hayashi, Y. (8) 290 Haynes, R.K. (3) 26 He, L. (1) 395 Healy, P.C. (1) 106; (3) 12 Hehert, N. (4) 47 Hecht, S.M. (6) 249, 251-253 Heckmann, G. (1) 416-420; (8) 194 Hedden, D. (1) 127 Heelis, P.F. (6) 177 Heesche, K. (1) 96 Hefetz, Y. (6) 248 Hefferman, G.D. (5) 174 Hegemann, M. (1) 327 Heikens, W. (6) 147 Hein, G. (1) 362; (4) 78 Hein, J. (1) 319, 348, 365 Heine, M. (7) 91 Heineke, D. (7) 31
Heinemann, U. (6) 147 Heinicke, J. (1) 278 Heitz, A. (7) 124 Helbing, J. (6) 146 Helene, C. (6) 209, 214 Helinski, J. (6) 105 Hellwinkel, D. (1) 169 Helquist, P. (7) 57 Hemling, M.E. (6) 294 Hendrickson, J.B. (1) 261 Henin, Y.(6) 13 Henkel, T. (8) 21 Hennawy, I.T. (7) 28 Hennet, S. (7) 121 Henriksen, L. (6) 73 Hepburn, T.W. ( 5 ) 230 Herberhold, M. (8) 147 Herbst-Irmer, R. (8) 202 Herdan, J.M.(5) 121 Herdewijn, P. (6) 18, 19, 21, 136 Herdtweck, E. (1) 165 Herranz, R. (6) 34 Herrmann, A.T. (1) 336 Herrmann, E. (1) 32 Herschlag, D. (6) 239 Herve, M.-J. (1) 285 Hesse, D. (7) 30; (8) 90 Heuer, L. (1) 202 Heus, H.A. (6) 216, 229, 232, 233 Higgins, K.M. (5) 292 Highcock, R. (6) 48 Higuchi, H. (6) 131 Hikosaka, T. (1) 120 Hilbers, C.W. (6) 215, 257 Hilbers, M.P. (6) 226 Hilderbrandt, W. (1) 101 Hill, D.T. (1) 16 Hill, M.N.S. (5) 293 Hillenkamp, F. (6) 248 Hilpert, H. (6) 48, 49 Hines, W. (6) 6 Hinkle, R.J. (1) 234 Him, A. (1) 219 Him, M. (6) 155 Hiort, C. (6) 310, 312 Hirai, K. (5) 272 Hirakawa, K. (7) 70 Hirama, M. (7) 96 Hirata, Y. (6) 177 Hiratake, J. (2) 1 1 Hiroaki, H. (6) 218, 231 Hirose, T. (8) 262 Hirota, K. (6) 50 Hirotsu, K. (1) 277, 310, 313, 3 15 Hirschbein, B.L. (4) 18; (6) 103
Organophosphorus Chemistry
368 Hirschowitz, W. (6) 67 Hitchcock, P.B. (1) 179, 332, 373, 388; (3) 33 Hoang, H. (7) 24 Hochberg, R. (7) 99 Hock, R. (7) 41 Hocking, M.B. (1) 381 Hodge, R.P. (6) 318 Hoenle, W. (1) 42 Hoffman, M. (5) 169, 170 Hoffmann, J. (1) 204, 331 Hogarth, G. (1) 176 Hohenwarter, K. ( I ) 405 Hokelek, T. (8) 295 Holand, S. (I) 399, 403 Holley, W.K. (8) 91 Holrnes, C.E. (6) 252 Holmes, J.M. (2) 1, 5, 6, 20 Holmes, R.R. (2) 1, 5, 6, 18, 20 Holy, A. (6) 21-24, 26, 31 Hon, Y.4.(7) 40 Honda, T. (8) 74, 75 Hoogmartens, J. (6) 18 Hope, H. ( I ) 55, 56 Hopkins, P.B. (6) 286, 287 Hori, T. (5) 69 Hormi, O.E.O.(5) 131 Horn, H. (1) 295 Hornbuckle, S.F. (7) 1 Hosaka, H. (4) 54, 55; (6) 70, 92 Hosmane, N.S. (1) 27; (4) 24 Hosoda, A. (5) 280 Hosoda, M. (6) 273 Hosona, H. (6) 50 Hostetler, K.Y.(6) 16 Howell, H.G. (6) 27 Hoyle, C.E. (8) 250 Hrebabecky, H. (6) 22 Hruska, F.E. (6) 167 Hu, B.-F. ( 5 ) 58, 81 Huang, D.-L.(6) 8 Huang, L.M. (8) 209 Huang, N.Z. (7) 80 Huang, T.T.-S. ( I ) 147 Huang, Y .-2. (7) 29 Huang, Z. (6) 133 Huber, E.W. ( I ) 155 Huch, V. (1) 195; (7) 36 Hudson, H.R. (5) 88 Huff, J.R. (5) 36 Hughes, A.N. (1) 404 Hughes, N.A. (5) 293 Hund, H. (8) 41 Hund, R.D. (8) 34, 35 Hursthouse, M.B. (7) 62 Husek, A. (5) 7 4 Huskens, J. (6) 65, 132
Hussoin, M.S. (1) 261 Huszthy, P. (1) 190 Huttner, H. ( I ) 266 Huy, N.H.T. (1) 389 Huynh-Dinh, T. (6) 13 Hwang, C.-K. (6) 264; (7) 119 Hyatt, E.M. (4) 27; (5) 18 Iden, C.R. (6) 68, 69, 156 Igau, A. (1) 192 Ignat’eva, S.N. (1) 289, 299, 300, 302 Igolen, J. (6) 205 Iguchi, S. (1) 222 Ihara, T. (6) 275, 282 Iimura, S. (6) 3 Iino, Y. (7) 105; (8) 58, 60 Iishikawa, K. (6) 72 Ikegami, S . (8) 74, 75 Ikehara, M. (6) 218 Ikuta, S. (6) 166, 321 Imada, T.(6) 87, 88 Imai, S. (6) 36 Imamoto, T. (1) 119, 120; (3) 17 Iman, M. ( I ) 256 Imbach, J.-L. (6) 102, 148, 149 Imhoff, P. (8) 92, 200, 201 Inamoto, N. (1) 180, 310, 312; ( 5 ) 294 Indzhikyan, M.G. ( I ) 65, 94, 140, 141, 235; (5) 87 Inobushi, A. (8) 275-278 Inoguchi, K. (1) 72, 90 Inoue, K. (8) 137, 157, 213 Insubushi, A. (8) 237 Ionin, B.I. (5) 256, 260 Ionkin, A.S. ( I ) 287-290, 299-303; (5) 257 Iorish, V.Y.(4) 37 Iovleva, M.M. (8) 257, 273 Iribarren, A. (6) 143, 144 Ironside, M.D. (3) 21 Irwin, W.J. (5) 182 Ishigami, K. (1) 161 Ishikawa, N. (8) 114-1 16, 180 Ishizaki, T. (6) 80, 271 Ishmaeva, E.A. (1) 342; (8) 17 Ishmuratov, A S . (5) 46 Islam, M.S. (8) 208 Islamov, R.G. (5) 202 Ismagilov, R.K. (5) 123 Issleib, K. (1) 97 Ito, S. (7) 96 Ito, Z. (8) 154, 228 Ivanchenko, V.I. (1) 292 Ivanov, A.N. (5) 8
Ivanova, N.A. (8) 257 Iverson, P.L. (6) 106 Ivonin, S.P. (1) 130 iwai, S. (6) 89 Iwasaki, F. (7) 16 Iwasawa, N. (7) 118 Iyer, N. (6) 14, 15 Iyer, R.P. (6) 101, 111 Izso, G. (1) 190 Jaarsveld, K. (3) 29 Jachow, H. (1) 49, 51 Jackson, R.F.W. (5) 154 Jacob, P. (4) 31; (5) 103 Jacobson, K. (6) 66 Jacobson, R.A. (4) 27; (5) 18 Jacquier, R. (5) 216, 217 Jaeger, G. (5) 52 Jaeger, L. (8) 153 Jaeggi, K.A. (5) 253 Jagowski, A.J., jun. (8) 229 Jakubik, D. (1) 88 Jamieson, L.A. (5) 130 Janakiraman, M.N. (4) 27; (5) 18 Janati, T. (1) 326 Jand, J. (1) 369; (8) 113 Janecki, T.(4) 5; (5) 134 Jankowski, S. (5) 77 Jansen, J.F.G.A. ( I ) 77 Jansen, M. (7) 99 Janssen, A. (4) 7 8 Janssen, G. (6) 18 Jaques, J. (5) 11 Jarmer, M. (1) 35, 36, 38, 39, 203 Jarvi, E.T. (3) 5; (6) 45; (7) 60 Jaseja, M. (6) 245 Jastorff, B. (4) 44;(5) 27 Jaud, J . (1) 284 Jaworska, D. (5) 197 Jedlinski, Z. (8) 142 Jekel, A.P. (8) 129 Jenkins, I.D. (1) 106; (3) 12 Jenkins, M.J. (7) 81 Jhurani, P. (6) 7 4 Ji, Y. (6) 17 Jia, X. (6) 305 Jiaqi, P. (7) 44 Jie, L. (6) 19 Jin, G. (1) 392 Jina, A.N. (5) 42 Jinkerson, D.L.(8) 4 Johns, D.G. (6) 21 Johns, R.B. (4) 39-41; (5) 21-23, 75 Johnson, F. (6) 68, 69, 153, 156
369
Author Index Johnson, J.W. (5) 1 18 Johnson, L.K. (7) 32 Johnson. M.P. (4) 23, 25 Johnson, M.R. (5) 28 Johnson, P. (6) 309 Johnson, R.K. (1) 16 Johnson, R.L. (5) 227 Johnston, G.A. (5) 228 Jones, A.S. (6) 12 Jones, P.G. (1) 202; (2) 9 , 19 Jones, R.A. (1) 52-54, 57; (6) 162-164, 21 1 Jones, R.C.F. (7) 58 Jones, R.H. (1) 24 Jones, S. (1) 95 Jordan, S. (6) 146 Joseph-Nathan, P. (2) 2 3 Joyce, G.F. (6) 242 Jubault, M. (7) 65 JugC, S. (1) 1 1 8; (4) 4, 36; (5) 206 Jung, K.-Y. (2) 16, 17; (5) 185; (7) 122 Jung, M. (1) 73 Jurkschat, K. (5) 298 Just, G. (4) 47; (6) 39 Jutzi, P. (1) 135, 371 Kabachnik, M.1. (1) 265; (8) 78 Kabata, H. (6) 35 Kabela, J . (8) 184 Kadoura, J. (8) 66 Kaehlig, H. (5) 171, 224 Kagan, H.B. (3) 10 Kahne. D. (6) 268 Kaji, A. (6) 131 Kajihara, K. (1) 255 Kajiwara, M. (8) 140, 238, 239, 245, 263 Kakiuchi, H. (8) 63 Kalabina, A.V. (8) 196 Kalashnik, A.T. (8) 255, 256 Kalchauser, H. (5) 291 Kalibabchuk, V.A. (8) 205, 298 Kalish, V.J. (7) 80 Kalman, A. (1) 400; (3) 13 Kamalov, R.M. (5) 202 Kameda, M. (1) 166 Kamenecka, T.M. ( 5 ) 184 Kamiya, Y. (8) 262 Kamokari, M. (8) 9 8 Kan, L. (5) 289 Kan, L . 4 . (6) 208 Kanamathareddy, S. (5) 155 Kanaoka, Y. (6) 207 Kanavarioti, A. (6) 7 Kandile, N.G. (1) 144
Kaneko, C. (5) 262 Kaneko, M. (8) 9 8 Kann, N. (7) 57 Kanomata, N. (8) 59 Kanzaki, M. ( I ) 255 Kapoor, P.N. (1) 179 Kappe, T. (8) 95 Kappen, L.S. (6) 258, 259 Karaghiosoff, N. (1) 390 Karanewsky, D.S.(5) 115; (7) 53 Karasik, A.A. (1) 197 Kardos, N. (5) 206 Karelson, M. (6) 181 Karev, V.N. (1) 11 1 Karim, S. (7) 97 Karkozov, V.G. (8) 183 Karpacheva, S.N. (1) 124 Karplus, M. (6) 329, 330 Karpunina, L.B. (2) 26 Karsch, H.H. (1) 62; (7) 34 Karthikeyan, S. (8) 152 Kashemirov, B.A. (5) 252 Kasheva, T.N. (5) 208, 209 Kashiwabara, K. ( I ) 73 Kaska, W.C. ( I ) 80 Kasparek, F. (5) 74 Kasukhin, L.F. (5) 45 Katagiri, N. (5) 262 Kataoka, S. (6) 36 Kato, H . (8) 6 3 Kato, M. (6) 36 Kato, R. (4) 56; (6) 71 Katritzky, A.R. (5) 118; (6) 181; (7) 114 Katti, K.V. (1) 247; (8) 69, 84, 199, 202, 203 Katzenbeisser, U . (1) 33 Kaukorat, T. (2) 9 Kaur, T. (8) 31 Kawada, T . (6) 36 Kawade, T. (6) 35 Kawai, S.H. (6) 39 Kawai, Y. (1) 330 Kawanishi, K. (5) 69 Kawasaki, M. (7) 6 Kawashima, M. (6) 92 Kawashima, T. (1) 180; (5) 294 Kawate, H. (8) 63 Kazakov, P.V. (5) 128, 129 Kazankova, M.A. (1) 182 Kazantseva, M.V.( I ) 220 Kazantseva, V.V. (8) 225 Kean, J.M.(6) 130 Keana, J.F.W. (5) 137 Keck, H. ( I ) 352; (4) 66 Keenan, R.W. (5) 37 Keglevich, G. (1) 400: (3) 13
Kellner, K. (1) 133 Kemmitt, R.D.W. (3) 34 Kempener, Y. (6) 152 Kemper, B. (6) 221 Kenan, W.R. (1) 158 Kennepohl, D.K. (2) 32, 33 Kennewell, P.D. (7) 101; (8) 53 Kenyon, G.L. (6) 6 Kerdel, K. (5) 63 Kergaye, A.A. (5) 305 Khachatryan, R.A. (1) 65, 94, 235 Khalil, F.Y. (1) 251, 252 Khalil, K.M. (7) 28 Khan, M. (5) 304 Khanous, A. (7) 64,65 Kharchenko, A.V. (1) 130 Khaskin, B.A. (5) 46 Khistich, A.I. (8) 76 Khodyrev, B.S. (8) 253 Khokhlov, P.S. (5) 252 Khorana, H.G. (7) 7 8 Khusainova, N.G. (5) 257, 258 Kibardin, A.M. (1) 41 1; (4) 35 Kierzek, R. (6) 179, 180 Kikuchi, T. (7) 16 Kikuoka, M. (1) 184 Kilic, A. (8) 126, 145 Kilic, Z. (8) 126, 295 Kim, C. (8) 135, 139, 232, 233 Kim, C.U. (6) 20, 2 8 Kim, J.N. (1) 146 Kim, S. (4) 23 Kim, S.K. (6) 312 Kim, T.C. (1) 369, 370; (4) 70, 71 Kim, T.V. (5) 93, 147, 148, 254 Kimura, Y. (1) 238, 263 Kirchner, J.J. (6) 286, 287 Kirchner, M.B. (5) 268 Kireen, V.V. (8) 218 Kisalus, J.C. (1) 413 Kiseleva, E.I. (5) 93, 147, 148, 254 Kishida, E. (8) 73 Kitade, Y. (6) 50 Kitagawa, K. (8) 285 Kitani, A. (6) 44 Kitas, E.A. (5) 25 Kitayama, M. (8) 172 Klarner, F.-G. (1) 407; (3) 8; (7) 41 Klein, H.-F. (8) 36 Klepa, T.I. (1) 112 Klicic, J. (5) 16 Kline, P.C. (6) 150 Klingebiel, U . (1) 30 Klobucar, W.D. (8) 241, 242
370 Knight, D.A. (1) 20 Knobler, C.B. (1) 138 Knorr, R. ( 5 ) 25 Knudsen, K.L. (1) 404 KO, Y.Y.C.Y.L. (1) 297 Kobayashi, N. (5) 272 Kobayashi, T. (8) 63, 9 8 Koch, T.H. (6) 172 Koch, V.R. (8) 236 Kochendorfer, F. (7) 99 Kochevar, I.E. (6) 248 Kodaka, M. (1) 162 Kodama, G. (1) 166 Kodama, H. (6) 231 Koehler, H. (8) 153 Kollemann, C. (1) 246 Koenig, H. (8) 36 Koenig, M. (1) 284, 285 Koerner, J.F. (5) 227 Koster, H. (6) 187 Koev, I.G. (8) 141 Koga, M. (6) 142 Kohda, K. (6) 288 Kohn, H. (6) 269 Koidan, G.N. (1) 216, 291; (4) 26; (8) 82 Koizumi, M. (6) 235 Koizumi, T. (5) 229; (8) 285 Kokubo, I. (5) 279 Kolbina, G.F. (8) 272 Kolesnik, N.P. (1) 67; (5) 112 Kolich, C.H. (8) 241, 242 Koll, 8. (1) 45 Kolmel, C. (1) 295 Kolodka, T.V. (4) 33 Kolodyazhnyi, 0.1. (1) 137; (4) 19, 20; (5) 251; (7) 2 Kolomnikova, G.D. (5) 45 Komarov, V.Ya. (5) 245 Korniyama, M. (6) 9, 35 Komori, T. (8) 115 Kondo, S. (1) 239 Konieczny, M. (5) 155 Konovalova, I.V. (2) 8, 13-15; ( 5 ) 17 Kook, L.H. (6) 38, 132, 226, 244, 245 Kooreman, P.A. (4) 45 Kopylova, L.Yu. (5) 123 Korenchenko, O.V. (5) 188, 303 Korf, U. (6) 43 Korkin, A.A. (4) 68; (8) 9, 10, 78 Korneeva, E.V. (8) 272 Kornilov, M.Yu. (5) 147 Kostka, K. (5) 165 Kosuge, S. ( I ) 222 Kotaka, T. (8) 252
Organophosphorus Chemistry Kouchakdjian, M. (6) 183, 184 Kouril, M. (8) 184 Kovacs, I. (1) 278 Kovalenko, L.V. (5) 128, 129 Kovaleva, T.V. (5) 111 Kowalski, M.H. (1) 234 Koyanagi, S. (7) 70 Kozarich, J.W. (6) 256, 258, 259 Kozawa, H. (1) 250 Kozikowski, A.P. ( 5 ) 38, 39 Kozlov, E.S. (1) 130 Kozlova, E.V. (5) 208 Krachinin, N.P. (8) 255 Kramer, B. (1) 273 Krannich, L.K. (1) 11 Krawchik, E. (5) 261 Krawiecka, B. (5) 92 Krebs, B. (1) 307 Krech, F. (1) 97 Kreitmeier, P. (1) 316, 318 Kren, R.M. (1) 368; (5) 241 Kretschmer, U. (6) 126, 127 Kriger, U. (7) 14 Krishnamurthy, S.S. (2) 18; (4) 24; (8) 20, 152 Krishnan, B.R. (5) 5 Krol, E.S. (5) 267 Kroona, H.B. (5) 227 Kroos, R. (1) 135, 371 Kross, M. (8) 156 Kroto, H.W. (1) 323 Kruger, C. ( I ) 88, 335, 336; (7) 41 Kriiger, U. (1) 328, 343; (4) 79; (8) 32 Kruger, T.L. (1) 100 Krulle, T. (7) 73 Krylova, V.N. (5) 32 Krzyzanowska, B. (5)61 Kuhiniok, S. (1) 210 Kuho, A. (8) 106 Kubota, T. (8) 282 Kubota, Y. (6) 280 Kucera, L.S. (6) 14, 15 Kuchen, W. (1) 86, 219, 352, 362; (4) 66, 78 Kucherova, M.N.(8) 96 Kudryavtsev, A.A. (4) 26 Kudryavtseva, L.I. (5) 142 Kuhn, A. (1) 201 Kuhn, N. (1) 201 Kuijpers, W.H.A. (6) 65, 132 Kukhar, V.P. ( I ) 137; ( 5 ) 190, 208, 209 Kukubo, I. (5) 278 Kukushkin, V.Yu. (1) 248; (8) 44
Kulagowski, J.J. (5) 36 Kulichikhin, V.G. (8) 253, 258-260, 272 Kulishov, Y.G. (3) 14 Kulkarni, D.G. (1) 148 Kumagawa, Y. (7) 112 Kumar, A. (6) 12 Kumar, D. (8) 131 Kumar, P. (6) 64,202 Kumar, R. (1) 29 Kumaravel, S.S. (2) 18; (8) 20, 187 Kumberger, 0. (8) 16 Kung, P.-P. (6) 21 1 Kunisada, H. (1) 239 Kunugi, S. (6) 35 Kuo, E.E. (6) 97 Kuptsov, S.A. (8) 256 Kurachi, Y. (8) 238, 239 Kurahashi, A. (8) 163, 166, 168, 172 Kurakake, T. ( I ) 267 Kuraki, Y. (8) 281, 282 Kurchenko, L.P. (8) 11 1 Kureno, Y. (5) 300 Kurg, V.V. (1) 260 Kurihara, T. (5) 107; (8) 56 Kurts, A.L. (1) 150 Kurtz, S.K. ( I ) 126 Kusano, T . (5) 10 Kushlan, D.M. (6) 220 Kusumoto, T. (3) 17 Kuz’mina, N.Yu. (1) 103 Kuznetsova. A.A. (1) 220 Kuznetsova, N.A. (8) 96 Kuznetsova, S.A. (5)4 5 Kwazoe, Y. (6) 288 Kwik, W.L. (8) 93, 9 4 Kwok, T.J. (4) 22 Kwon, S. (8) 212, 291, 296 Labarre, J.F. (8) 113, 122-125, 156 Labelle, M. (7) 87 Labuda, D. (6) 237 Lachkova, V. ( 5 ) 249 Lacombe, S . (1) 324 Lafitte, J.A. (1) 118; (4) 36 Lahti, M. (6) I 1 Lamandk, L. (1) 367 Lamm, G.M. (4) 51; (6) 197 Lammertsma, K. (7) 3; (8) 8 Larnond, A.I. (6) 91, 143 Lampe, D. (5) 51 Landini, D. (8) 158 Landry, C.J.T. (8) 284 Lang, H.(1) 321, 322
37 1
Author Index Lang, S . (1) 41 Lange, L. (1) 210 Langen, H. (8) 283 Langer, R. (8) 235 Langhauser, F. (1) 336 Langley, D.R. (6) 260 Lanssen, A. (1) 362 Laretina, A.P. (8) 78 Larpent, C. (1) 191, 230, 231 (3) 2 Laszkiewicz, B. (8) 141 Latscha, H.P. (7) 13 Lattes, A. (5) 63, 97 Lauchmann, J. (1) 164 Laurent, C. (1) 206 Laurent, Y. (8) 215, 224 Lavery, R. (6) 332 Lavetina, A.P. (5) 129 Lavilla, R. (7) 77 Layher, E. (1) 43 Lazanova, R.A. (8) 141 Lazhko, E.I. (1) 182 Leader, H. (5) 274 Leake, E. (6) 14 Lecomte, L. (1) 186 Lee, A.L. (1) 162 Lee, F.K.(1) 221 Lee, H. (6) 155, 309 Lee, J.N. (8) 287 Lee, K. (5) 181 Lee, S. ( 5 ) 230 Lee, Y.F. (2) 33 Lee, Y.H. (5) 105 Leeson, P.D. (5) 41 Lefeber, A.W.M. (5) 138 Lefkaditis, D.A. (7) 27 Le Floch, P. (1) 9, 282, 283, 401
Le Goffic, F. (5) 198 Leichtweis, I. (8) 88 Leise, M. (1) 321, 322 Lellouche, J.-P. (7) 85 Le Merrer, Y. (7) 84 Lemmen, P. (4) 46; (5) 43 Lemos, M.A.N.D.A. (1) 332 Lempert, K. (1) 190 Lemon, I.C. (5) 41 Lenting, H.B.M. (6) 16 Lenz, R.W. (8) 210 Leonardo, C.L. (8) 7 Leong, W.R. (8) 94 Leont’eva, I.V. (1) 265 Lepre, C.A. (6) 301 Lekontov, S.A. (5) 2, 3; (8) 86 Leroux, Y. (5) 297 Leserman, L. (6) 138 Leslie, D.R. (5) 91 Lesnikowski, Z.J. (6) 37
L’Esperance, R.P. (1) 122 Letsinger, R.L. (6) 62 Leung, P.H. (1) 187 Leusen, F.J.J. (5) 79, 80 Le Van, D. (1) 307, 327 Levina, A.Ya. (1) 41 1; (4) 35 Levine, J.A. (5) 70 Levis, J.T. (6) 130 Lewis, T. (5) 174 Lho, D.S. (5) 105 Li, C. (5) 106 Li, G. (1) 395; ( 5 ) 106 Li, J. ( 5 ) 277 Li, S.-Y. (7) 40 Li, V . 4 . (5) 96; (6) 269 Li, X. (6) 174 Li, Y.-G. (5) 141 Li, Y.F.(6) 178 Li, Z.-H. (5) 166 Liang, M. (8) 222 Liao, Q. (1) 258 Liao, X. (5) 140 Liao, Y. (7) 29 Lidon, M.J. (8) 51 Lie, L. (6) 18 Lieberknecht, A. (7) 74 Lieberman, J. (8) 33, 204 Lieske, C.N. (5) 268 Lim, C. (6) 329, 330 Lindeman, S.V. (5) 299 Linden, A. (8) 20 Lino, Y. (8) 3 Linti, G. (1) 357 Lippard, S.J. (6) 301 Lippert, B. (6) 45 Lipshutz, B.H. (1) 154 Litinas, K.E. (7) 27 Litkei, G. (8) 52 Litten, J.C. (1) 236; (7) 37 Litvinov, 1.A. ( I ) 291; (8) 258 Liu, H.-J. (7) 116 Liu, K. (2) 11 Liu, L. (1) 395 Liu, M. (1) 286 Liu, P.-K. (7) 61 Liu, S.-T. (1) 83 Liu, Y.-S. (5) 141 Liu, Z. (1) 215; (5)47 Liu, 2.-P. (7) 4 Livantsov, M.V. (1) 183, 214; (2) 22; (4) 15; (5) 213 Live, D.H. (6) 210 Liversidge, G.G. (8) 274 Liverton, N.J. (5) 41; (7) 98 Llamas-Saiz, A.L. (8) 54 Lochschmidt, S . (1) 366 Lodwig, C. (1) 407; (3) 8 Liinnherg, H. (6) 10, 11
Liinnecke, P. (4) 81 Loginova, I.V. (2) 13 Logunov, A.P. (1) 102, 103 Logusch, E.W. (5) 221 Long, E.C. (6) 251, 278 Lopez, L. (1) 344, 397, 398; (4) 76; (8) 191, 192 Lopusinski, A. (5) 4 Lorenzen, D. (1) 219 Loschner, T. (6) 129 Losse, G. (6) 94 Low, D. (7) 15 Lowe, G. (6) 56, 57 Lown, J.W. (6) 170, 276 Lu, K.-J. (1) 27 Lu, L. (7) 40 Lu, P. (6) 67 Luche, J.L. (1) 149 Ludwig, J. (6) 51 Lucke, E. (1) 306 Lucke, J. (8) 223 Liiking, S. (4) 63; (6) 145 Luth, B. (1) 327 Luetkens, M.L. (1) 10 Luh, B.Y. (6) 20, 28 Luheshi, A.-B.N. (7) 101; (8) 53 Lukashev, N.V. (1) 182 Luk’yanenko, S.N. (4) 34; (5) 255 Lumbroso, H. (1) 376 Lumin, S. (7) 86 Lutsenko, I.F. (4) 15; (5) 213 Luu, B. (6) 17 Luu, R.P.T. (4) 64 Luzikova, E.V. (1) 182 Lyashenko, Yu.E. (1) 212, 213 Lynch, V.P. (5) 88 Ma, X.-B. (1) 394 Ma, Y . - X . (4) 61; (6) 121, 125 Maas, G. (1) 204 Maasa, W. (1) 402 McBeath, R.J. (6) 169 McCarthy, J.R. (3) 5; (7) 60 Maccioni, A . (8) 158 McClard, R.W. (5) 117 McClure, C.K. (2) 16, 17; (5) 185; (7) 122 McCollum, C. (6) 66 MacDairmid, J.E. (6) 33 MacDonald, H.R. (6) 195 McDonnell, G.S. (8) 101, 217, 268 McElroy, A.B. (3) 19 McEwen, W.E. (1) 249 McFadyen, W.D. (6) 309 McFarlane, H.C.E. (1) 85
372 McFarlane, W. (1) 85, 95 McGall, G.H. (6) 256 McGrath, J.E. (3) 16 McInally, T. (4) 3; (5) 120 McKellar, R.B. (6) 5 McLennan, A.G. (6) 54 MacMillan, A.M. (6) 158, 159 McNemar, L. (6) 6 McQuaid, L.A. (5) 219 McQuire, L. (3) 21 Maeda, H. (1) 184; (6) 328 Maeno, N. (5) 229 Maerker, A. (1) 18 Markl, G. (1) 316, 318, 405-408; (3) 8 Maestro, M.M. (3) 24 Mag, M. (4) 63; (6) 145 Magill, J.H. (8) 216 Magliozzo, R.S. (6) 250 Magnusson, E. (2) 2 Mague, J.T. (4) 25 Mahajna, M. (5) 273 Mahran, M.R. (5) 284 Mai, G. (7) 111 Maia, A. (8) 158 Maib, P. (7) 11 1 Maidanovich, N.K. (8) 97 Maier, L. (5) 114, 189, 191, 192, 200, 201, 220 Majewski, P. (1) 145 Majoral, J.-P. ( I ) 170, 349; (5) 65, 246, 247, 248 Majumdar, C. (6) 112 Mak, T.C.W. (1) 25 Makarov, G.M. (5) 202 Makenzie, L. (6) 294 Makhaeva, G.F. (5) 46 Maki, T. (1) 184 Maki, Y. (6) 50 Malavaud, C. ( 1 ) 344; (4) 76 Malenko, D.M. (4) 34; (5) 145, 146, 255 Maligres, P. (3) 6; (4) 6 Malik, M. (5) 212 Malik, P. (8) 159 Malinovskii, T.I. (5) 301 Malkova, G.Sh. (5) 187 Malley, M.F. (7) 53 Malygin, V.V. (5) 46 Malysheva, S.F. (1) 92, 93, 159 Malyutina, I.V. (1) 112 Marndapur, V.R. (1) 163 Manchilova, S. (5) 263 Mangeney, P. (4) 28 Manginot, E. (7) 48; (8) 67, 83 Mann, A. (7) 17 Manners, 1. (8) 101, 160, 198, 222, 246, 268
Organophosphorus Chemistry Mannik, J.H. (6) 277 Mantlo, N.B. (7) 118 Marasco, C.J., jun. (6) 15 Marchand, R. (8) 215, 224 Marchenko, A.P. (1) 216, 291; (2) 31; (4) 26; (8) 77, 82 Marco, C. (8) 251, 254, 261 Marder, T.B. (1) 126 Mardones, M.A. (1) 27, 52, 53, 57 Marecek, A. (8) 81 Marecek, J.F. (5) 34, 35, 40 Marfey, P. (6) 141 Mariano, P.S. (5) 230 Marinelli, E.R. (6) 69 Marinetti, A. (1) 9, 283, 304, 305, 373 Markovskii, L.N. (1) 67, 279, 281, 292, 342, 345-347; (4) 67, 69, 73, 75; (5) 112, 301; (8) 17, 30 Markowska, A. (5) 44 Marlin, J.E. (3) 27 Marquez, V.E. (5) I66 Marretta, J. (5) 186 Marsch, M. (7) 51 Marshall, W.S. (6) 125 Marsimov, A.S. (8) 218 Marsters, J.C. (6) 74, 192 Martin, J.C. (6) 20, 27, 28 Martin, R. (1) 101 Martin, S.F. (1) 153 Martinez, J. (7) 123, 124 Martynov, I.V. (1) 212, 213; (5) 2, 3, 8, 46, 188, 256, 303; (8) 86 Martynyuk, E.G.(5) 1 1 1 Marumoto, R. (6) 254 Maruyama, I. (8) 154, 228 Marzilli, L.G. (6) 304, 305 Masarnune, S. (7) 92 Mascerenas, J.L. (3) 25 Mashima, K. (1) 17 Mason, S. (3) 34 Masotti, H. (4) 64 Mastalia, A. (5) 153 Mastryukova, T.A. (1) 265; (5) 128, 129, 178 Masuda, S. (8) 276 Masui, M. (1) 184, 241 Mataga, N. (6) 177 Matejec, R. (8) 283 Matern, E. (1) 34, 36, 38, 203 Mathey, F. (1) 7-9, 282, 283, 304, 305, 373, 378, 380, 383, 389, 399, 401, 403 Mathieu, R . (1) 177 Matos, R. (1) 308
Matoshko, G.V. (8) 96 Matsui, M. (5) 229 Matsuki, T. (8) 288 Matsukura, M. (6) 111, 113, I15 Matsumoto, J . (8) 6 4 Matsurnoto, K. (1) 382 Matsurnoto, Y. (6) 9 Matsurnura, Y. (1) 17 Matsuura, T. (6) 255; (7) 90 Matt, D. ( I ) 26 Matthews, D.P. (3) 5 ; (7) 60 Matuszewski, B. (5) 84 Matveeva, E.D. (1) 150 Matyjaszewski, K. (8) 207, 220, 22 1 Matzen, M. (6) 146 Mawer, I.M. (5) 36 Mayer, H.A. ( I ) 80 Maynard, S.J. (8) 107, 108 Mazerolles, P. (1) 206 Mazibres, M.-R. ( I ) 281, 369, 370, 391; (4) 70, 71, 73, 74 Mazumder, A. (6) 247 Mazzah, A. (8) 204 Meares, C.F. (6) 9 8 Mebel, A.M. (8) 9 Medvedeva, L.Ya. (8) 188, 297 Meehan, E.J. (5) 304 Meetsma, A. (8) 129, 187 Mehrotra, R.C. (5) 55 Meidine, M.F. ( I ) 308, 332, 348 Meier, H. (4) 7; (5) 125 Meignan, G. (1) 191, 230, 231; (3) 2 Meirovich, R. (5) 193 Meline, R.L. (3) 35 Mencl, J. (8) 184 Mendel, D. (6) 96 Menger, F.M. (6) 325 Menu, H.-J. (3) 32 Menu, M.-J. (8) 36, 117 Mercier, A. (5) 215 Mercier, F. (1) 378, 380 Mergny, J.-L. (6) 214 Merino, I. ( I ) 237, 253; (7) 22, 50; (8) 62 Merka, A. (6) 22 Merker, R.L. (8) 216 Merrirnan, M.C. (4) 53; (6) 246 Merwin, L.H. (5) 214 Metschies, T. (4) 44;(5) 27 Metternich, H.J. (1) 358 Metz, B. ( I ) 402 Meunier, B. (6) 289-29 1, 293 Mewett, K.N. ( 5 ) 228 Meyer, A. (6) 148 Meyer, K.L. (6) 15
Author Index Meyer, M. (1) 30 Meyer, W . E . (8) 27 Miao, X.-L. (5) 141 Michalska, M. (5) 104 Michalski, J . (5) 261; (6) 105 Michel, F. (6) 241 Miginiac, L. (5) 194 Mikhailov, S.N. (6) 137 Mikheleva, G . A . (8) 257 Mikhno, I.L. (8) 76 Mikohjczyk, M. ( I ) 227; (7) 120 Mikroyannis, J . (5) 292 Milder, S.J. (6) 289 Miljkovic, D . A . (5) 293 Millard, J.T. (6) 287 Miller, M.J. (7) 8 0 Miller, P.C. (7) 52 Miller, P.S. (6) 130 Miller, R.W. (1) 298 Miller, T . A . (1) 154 Millet, J. (7) 88 Milstein, D. (1) 178 Minami, T . (3) 7; (7) 70 Minasyan, G . G . ( I ) 141 Minbaev, B . U . (5) 152 Minic, D.J. (5) 293 Minouni, N. (5) 133 Minto, F. (8) 105, 286 Mio, S. (7) 112 Mioskowski, C. (3) 4; (7) 17, 88 Mirkin, C . A . (8) 79 Mironenko, D . A . (5) 208 Mironov, V.F. (2) 8, 13-15 Miroshnichenko, V.V. (8) 82 Mirskova, A.N. (5) 108 Misco, P.F. (6) 28 Misiura, K. (4) 48; (6) 198 Misra, V. (6) 210 Mitchell, M.J. (6) 67 Mitchell, T.N. (1) 96 Mitlsuya, H. (6) 113 Mitovic, A . D . (5) 228 Mitsuda, N. (1) 180 Miyamoto, T. (8) 6 4 Miyano, M. (7) 89 Miyano, S. (5) 83 Miyasaka, T. (6) 29 Miyauchi, N. (6) 334 Miyazawa, M. (1) 79 Mizakh, L.I. (2) 26 Mizoguchi, K. (8) 262 Mlotowska, B. (5) 44 Mocerino, M. (1) 152 Modak, A.S. (4) 53; (6) 168, 169, 246 Modest, E.J. (6) 14, 15 Modranka, R. (5) 165
373 Modro, T . A . (5) 14, 78, 86 Miiller, U . (6) 187 Moezzi, A. (1) 355 Mohammad, T. (6) 295 Moiseev, A.I. (1) 248; (8) 42 Mok, C.-Y. (1) 323 Mokhov, V.M. (8) 183 Molina, P. (1) 151; (7) 102, 106, 108-1 10; (8) 7, 15, 43, 46,47, 49-5 1, 54, 55 Molko, D. (4) 59; (6) 84 Mollin, J . (5) 74 Momose, S. (1) 79 Moni, S. (8) 166 Monohan, J.B. (5) 119 Montague, R.A. (8) 220, 221 Montenay-Garestier, T . (6) 2 14 Montforts, F.-P. (7) 111 Montlo, D . (1) 177 Montoneri, E. (5) 136, 160; (8) 161 Moore, A.J. (7) 62, 63 Moore, M.F. (6) 142 Moore, M.R. (3) 34 Moran, J . (1) 125 Moravshaya, T.M. (8) 249 Morgan, R.J. (6) 31 1 Mori, T. (1) 239; (6) 255, 313 Motiarty, R.M. (2) 11 Morimoto, T. (1) 90 Morise, X. (5) 113 Moriya, K. (8) 140 Morr, M. (6) 147 Morris, K.B. (1) 236; (7) 37 Morris-Natschke, S.L. (6) 15 Morrison, H. (6) 295 Morton, G.O. (6) 267 Morvan, F. (6) 102 Moskva, V.V. (1) 217; (5) 123; (8) 190 Mougel, M. (6) 223 Moulton, K.M. (8) 265 Mourey, R.J. (5) 34 Mourino, A . (3) 24, 25 Mousa, H . A . H . (8) 6 8 Mouyssou, P. ( I ) 256 Mugge, C. (1) 97 Muller, A . (1) 135, 271, 272, 306, 416, 420 Muller, G. (1) 62; (8) 16 Mueller, J.E. (6) 221 Mueller, N. (5) 224 Muller, U . (1) 243; (8) 294 Muller, W . E . G . (6) 138 Muir, A.S. (1) 85 Mukaiyama, T. (1) 262 Mukundan, S., jun. (6) 304 Mulder, G.J. (6) 59
Mulekar, S.V. (5) 13 Muller, G. (1) 164; (7) 34 Mullis, K.B. (6) 77 Mundt, C. (8) 24 Munk, S . A . (6) 80, 271, 272 Munoz, A. (1) 367 Murafuji, T . (7) 16 Murahashi, E. (3) 2 3 Murayama, M. (1) 277 Murillo, A . (2) 23 Murkerjec, P. (8) 4 Murray, A . W . (3) 21 Murray, H.H.(1) 10 Murray, M. (5) 151, 292 Murray, R.W. (8) 264 Murty, V.S. (6) 249 Musin, R.Z. (5) 235 Musio, R. (4) 8 Musker, W.K. (1) 110 Muth, H.-P. (6) 47 Mutherarasan, R. (8) 274 Mutti, S. (4) 28 Muzyka, P.V. (8) 30 Myers, P.L. (6) 48 Mynott, R. (1) 335 Nadzan, A.M. (7) 19 Naesens, L. (6) 21 Naganova, E . G . (1) 280 Nagao, F. (1) 250 Nagaraju, C. (5) 12, 59 Nagase, S. (1) 267, 277 Nagata, R. (3) 23 Nagato, Y. (5) 9 4 Naidu, M.S.R. (5) 12, 59 Nai-jue, 2. (7) 107 Nakacho, Y . (8) 275-278 Nakamura, H. (6) 280 Nakamura, S. (7) 70 Nakamura, Y. (8) 56 Nakanaga, T . (8) 138, 237, 279 Nakane, H. (6) 50 Nakanishi, T. (6) 3, 93 Nakashima, H . (6) 29 Nakatsuka, M. (7) 9 4 Nakayama, H. (8) 293 Nakayama, K. (5) 15 Nakayama, T . A . (7) 7 8 Nam, T.T. (1) 32 Narnestnikov, V.I. (5) 159 Namura, A . (6) 35 Nanishi, K. (8) 293 Nanjundiah, B.S. (1) 148 Narasimhan, N.S. (7) 115 Narisada, M. (7) 90 Narula, C.K. (1) 167 Nasman, J.H. (5) 131
Organophosphorus Chemistry
374 Naso, F . (4) 8 Nasser, J . (5) 127, 225 Natalinio, B. (5) 119 Natchev, I.A. (5) 21 1 Navech, J. (4) 12; (5) 9, 48 Nazamov, I.S. (5) 235 Neeb, M.K.(1) 100 Nefkens, S.C.A. (8) 200 Neganova, E.G. (I) 68, 69 Negoita, N. (5) 121 Negrebetskii, V.V. (1) 124, 292; (8) 30 Neidlein, R. (5) 193 Neijman, E.W.J.F. (6) 257 Neild, J. ( I ) 128 Neilson, R.H. (8) 4 Nekhoroshkov, V.M. (1) 290, 299, 300; (5) 257 Nelson, J. (6) 124 Nelson, S.G.(5) 184 Nesterova, L.I. (4) 34; (5) 255 Neuman, A. (5) 297 Neuman, J.-M. (6) 13, 323 Neumann, B. (1) 31 1 Neumann, J.-M. (6) 205 Neuner, P. (6) 91 Newman, P.C. (6) 173-175 Newton, M.G. (5) 304 Newton, R.P. (6) 327 Ng, P. (6) 74 Ngo, D.C. (8) 80, 133 Nguyen, M.T.(1) 329, 363 Nicolaides, D.N. (7) 27 Nicolaou, D.C. (6) 266 Nicolaou, K.C. (3) 6; (4) 6; (6) 262, 264, 266; (7) 119 Nicotra, F. (7) 59 Niecke, E. (1) 207, 273, 308, 319, 339-341, 348, 358, 360, 365; (4) 1, 17; (8) 5, 28, 29 Niedermann, H.-P. (4) 7; (5) 125 Nief, F. (1) 383 Nieger, M. (1) 61, 70, 194, 273, 319, 341, 360; (4) 17; (5) 286; (8) 29, 197 Nielsen, J. (4) 61; (6) 120, 121 Niemann, J . (1) 294 Nietzschmann, E. (5) 298 Nifant’ev, E.E. (4) 37, 38 Niimi, T. (8) 99 Niitsu, T. ( I ) 312 Nikolaeva, N.V. (1) 290, 303 Nikonov, G.N. ( I ) 139, 197 Ninader, M.V. (7) 109 Nishikawa, S. (6) 331 Nishio, S. (5) 94 Nisikawa, Y. (8) 157
Nitta, H. (8) 137 Nitta, I . (6) 29 Nitta, M. (7) 105; (8) 3, 58-60 Nixon, J.F. (1) 308, 332, 348, 373, 388; (3) 33 No, B.I. (1) 1 1 1 Noble, S.A. (6) 49 Noda, I. (7) 98 Noda, N. (5) 37 Noda, T. (7) 96 Noel, C. (8) 210, 231 Noth, H. (1) 167, 316, 318, 357, 408 Nolte, U . ( I ) 311 Noltemeyer, M. (1) 58; (7) 30; (8) 33, 85, 88-90, 202, 203 Nomura, N. (8) 285 Nomura, Y,(8) 290 Noordik, J.H. (5) 80 Noort, D.(6) 59 Norden, B. (6) 310, 312 Norman, A.D. (4) 29, 30 Norman, N.C. (1) 200, 268 Normant, J.F. (4) 28 Novak, L. (7) 76 Novosad, J . (5) 285 Nowotny, M. (1) 402 Noyori, R. (1) 5, 108 Nuber, B. (1) 169, 405 Nugiel, D.A.(7) 119 Nunn, C.M. (1) 54, 57 Nurenkov, O.A. (5) 299 Nuretdinov, LA. (5) 236 Nuyken, 0. (8) 179, 198 Nwosu, V.U. (6) 173 Nyulaszi, L. (1) 278 Oae, S. (1) 168, 250 Ohon, R. (1) 151; (7) 106 Oda, Y. (6) 218 Odinets, I.L. (5) 128, 129 Oehler, E. (5) 167, 168, 291 Oehmigen, T. (1) 113, 114 Offen, P. (6) 294 Otitserov, E.N. (2) 8, 14 Oganesyan, A.S. (5) 45 Ogawa, T. (6) 92; (7) 16 Ogilvie, K.K. (6) 82 Ogino, K. (7) 103 Oh, D.Y. (5) 181 Oh, S.T. (8) 214 Ohkawa, K. (8) 288 Ohmori, H. (1) 184, 240, 241; (7) 8 Ohnama, M. (8) 60 Ohno, A. (1) 188 Ohnuma, M. (7) 105
Ohta, H. (1) 233 Ohtani, M. (7) 90 Ohtsuka, E. (6) 89, 235 Oivanen, M. (6) 10 Okada, Y. (3) 7 Okamo, T. (8) 102 Okamoto, A. (1) 277, 313 Okamoto, Y. (5) 10, 278-282 Okamura, T. (6) 177 Okamura, W . H . (3) 28 Okuma, K. (1) 233 Okuno, H. (1) 162 Olah, G.A. (4) 77; (5) 180; (7) 72 Oleinik, V.A. (1) 291 Olinski, R. (6) 302 Olsen, D.B. (6) 238 Ol’shevskaya, V.A. (1) 28, 279 Ono, A. (6) 208 Ono, K. (6) 50 Onoue, K. (1) 250 Onozawa, T. (3) 17 Onys’ko, P.P. (5) 93, 147, 148, 254 Oosting, G.E. (8) 151 Oppenheimer, N.J. (6) 58 Orgel, L.E. (6) 135, 307 Orpen, A.G. (1) 22, 173; (4) 21 Osankina, E . I . (5) 236 Oshikawa, T. (5) 177 Oshiki, T. (1) 119, 120; (3) 17 Osowska-Pacewicka, K. (8) 72 Ossola, F. (1) 59 Otrnar, M. (6) 22, 23 Oudai, 0. (6) 231 Ouzouris, D. (I) 387 Ovakimyan, M.Zh. (1) 65, 140, 141 Ovchinnikov, V.V. (2) 12; (5) 187 Ozaki, S. (5) 33 Ozaki, T. (4) 13 Ozegowski, S. (5) 122, 124 Paasch, J. (8) 44,48 Paasch, S . (7) 107 Padwa, A. (7) 1 Paetzold, P. (1) 207; (8) 28 Page, P. (1) 391; (4) 74 Pai, N.R. (5) 66, 99 Paiaro, G. (1) 143 Paillous, N. (6) 289 Paine, R.T. (1) 167, 357; (3) 35 Pajunen, E.O. (5) 131 Pakrysh, E.F. (8) 76 Pakulski, M. (1) 200, 268, 276 Palacios, F. (1) 237, 253; (7)
375
Author Index 22, 49, 50; (8) 2, 61, 62, 70 Palacios, S.M. (1) 63, 64 Palmer, B.D. (6) 309 Palmer, T.C. (6) 128 Palom, Y. (6) 166 Pandey, G. (1) 189; (3) 9 Pandey, S.K. (5) 55 Pandolfo, L. ( I ) 143 Panza, L. (5) 139; (7) 59 Papkov, S.P. (8) 255, 256 Pardi, A. (6) 216, 229, 232, 233 Parent, C. (8) 224 Park, J . (3) 22 Parkin, S. (1) 55 Parmee, E.R. (7) 97 Parvez, M. (8) 80, 118, 148, 149, 160, 296 Pascal, J . (1) 116; (3) 1 Pascal, R.A. (1) 121, 122 Paschal, J.W. (5) 219 Pasternack, R.F. (6) 292 Pasternak, A. (1) 91; (8) 19 Patel, D.J. (6) 183, 184, 210 Patel, D . V . (5) 222 Patel, N . (6) 312 Patin, H. (1) 191, 230, 231; (3) 2 Patois, C.(5) 132, 244; (7) 56 Patonay, T. (8) 52 Patonay-Peli, E. (8) 52 Patsanovskii, 1.1. (1) 342; (8) 17 Pattenden, G. (7) 117 Patt-Siebel, U. (8) 294 Pautard-Cooper, A. ( I ) 158 Pauwels, R. (6) 21 Pavel, G.V. ( I ) 104 Pavlov, P.A. (5) 264 Pederson, R.L. (4) 42; (5) 19 Pederson, S.F. (3) 22 Pedroso, E. (6) 63, 166 Peel, M.R. (6) 49 Pegram, J.T. (3) 20 Peiffer, G. (1) 109 Peisach, J . (6) 250 Pel, R.A. (8) 142 Pellerin, B. (1) 320 Pellieciari, R. (5) 119 Pellon, B. (8) 159 Peneory, A.B. (1) 63 Peng, S.-M. (1) 83 Penk, M. (1) 135 Pen’kovskii, V . V . (1) 275, 293 Pennanen, P. (5) 131 Pennington, W. (5) 155 Pbc’h, D. (6) 148, 149 Perera, S.D. ( I ) 19 Peresypkina, L.P. (5) 226 PCrez, C. (6) 34
Perez, J. (7) 108; (8) 46 Perez-Sestelo, J . (3) 25 Perich, J.W. (4) 39-41; (5) 21-24, 75 Perilleux, D. (6) 152 Perischetti, R.A. (6) 200 Perreault, J.-P. (6) 237 PerrCe-Fauvet, M. (6) 292 Persau, C. (1) 43 Pervukhina, I.N. ( I ) 124 Peshkov, A.F. ( I ) 181 Pestana, D.C. (1) 55, 56, 355, 356 Peters, K. (1) 71 Peterson, N.L. (5) 227 Petrie, M.A. (1) 355 Petrosyan, V.S. (1) 183, 214; (2) 22 Petrov, A . A . (5) 245 Petrov, G. (5) 249 Petrova, J . (5) 263 Petrovskii, P.V. (1) 28; (5) 129 Petrus, C. (5) 216, 217 Petrus, F. (5) 216, 217 Ptister-Guillouzo, G. (1) 285, 324 Pfleiderer, W. (6) 10, 107, 136-138 Philippe, C. (6) 223 Phillips, L.R. (6) 101 Pianka, M. (5) 88 Piantadosi, C. (6) 14, 15 Piantadosi, S. (6) 15 Piccialli, G. (6) 182 Piccirilli, J.A. (6) 239 Pieken, W . A . (6) 238 Pieles, U . (4) 51; (6) 143, 197 Pieper, U . ( I ) 30 Pietrusiewicz, K.M. (3) 31 Pilarski, B. (5) 1 1 8 Pinchuk, A.M. ( I ) 112, 216; (2) 30, 31; (4) 26; (8) 77, 82 Pine, S.H. (7) 24 Pinkerton, A.A. (1) 247; (2) 33; (8) 69 Piotto, M.E. (4) 62; (6) 123, 124, 320 Pipko, S.E. (4) 33 Pireh, D. (7) 89 Pisarnitskii, D.A. (1) 183; (2) 22 PitiC, M. (6) 293 Pitt, C.G. (2) 10 Plass, W . (1) 416, 418-420 Plate, N . A . (8) 258-260 Plenat, F. (1) 116, 259; (3) 1 Plotnikov, V.F. (5) 245 Pliickthun, A . (6) 296 Plvshevskii. S . V . 18) 119
Pochet, S. (6) 185, 205 Podda, G. (8) 158 Pogosyan, A . S . (5) 87 Pohl, S. (1) 210 Polborn, K. ( I ) 316, 318, 357,
408
Polniaszek, R.P. (5) 144; (7) 68 Polonskaya, L.Yu. (2) 26 Polubentsev, A . V . (1) 93 Polumbrik, O . M . (5) 301 Polyakov, A . V . (1) 28 Pombeiro, A.J.L. (1) 332 Pomerantz, M. (3) 15; (7) 5; (8) 14 Pon, R.T. (4) 52; (6) 170, 186 Pons, A. (6) 196 Pooranchand, D. ( I ) 189; (3) 9 Popov, A . V . (5) 2 Poppe, L. (7) 76 Porai-Koshits, M.A. (8) 297 Porchia, M. (1) 59 Porco, J.A., jun. (6) 263, 265 Porter, B. (7) 77 Portier, C. (6) 223 Potin, P. (8) 206 Potter, B.V.L. (5) 51 Povolotskii, M.I. (1) 112, 292, 346; (4) 33, 67, 69; (8) 30 Povsic, T.J. (6) 212 Power, P.P. (1) 55, 56, 353, 355, 356 Powis, G. (5) 38, 39 Prakash, A . S . (6) 284 Prakasha, T.K. (4) 24 Prashed, M. (5) 212 Pratviel, G. (6) 293 Prestwich, G.D.(5) 34, 35, 40 Prikhod’ko, Yu.V. (1) 104 Pringle, P.G. (1) 98; (4) 21 Priol, J . ( I ) 191 Prishchenko, A . A . (1) 183, 214; (2) 22; ( 4 ) 15; (5) 213 Pritzkow, H. (1) 242, 296, 343; (7) 13, 14; (8) 32 Prouse, L.J.S. (1) 128 Priitz, W.A. (6) 317 Pruitt, J.R. (5) 184 Pucher, S.R. (8) 212, 227 Pudovik, A . N . (1) 105, 41 1; (2) 8, 13-15, 24; (4) 35; (5) 17, 202, 235, 257, 258 Pudovik, M.A. (5) 202 Pudovik, N . A . (2) 24 Puglisi, J.D. (6) 224, 225 Pujari, M.P. (5) 71 Purdy, A.P. (2) 10 Pushin, A . N . (5) 2 Pvle. A.M. (6) 313
376 Pyykko, P. (8) 6 Qing, B. (5) 58 Qu, Y. (6) 308 Quella, F. (8) 179 Quin, G.S. (1) 359; (5) 77, 269 Quin, L.D. (1) 359, 413; (5) 76, 77, 269, 273 Raben, A. (6) 14 Rachon, J . (5) 199 Radhakrishnan, 1. (6) 210 Ragan, J.A. (7) 94 Ragskaya, G.M. (8) 218 Raguveer, K.S.(8) 208 Rahrnan, M.F. (5) 85 Rakhrnatulina, T.N. ( I ) 92, 93, 159 Rakov, I.M. (5) 3 Ralitsch, M. (7) 116 Ralph, J . (5) 42 Rarnachandran, K. (7) 77 Rarnli, E. (5) 304 Rarnstein, J . (6) 332 Randina, L.V. (5) 145, 146 Rani, B.R. (5) 85 Rao, K.E.(6) 276 Rao, M.V. (6) 90 Rao, N.S. (1)413 Rao, R.J. (5) 54 Ratovskii, G.V. (1) 220 Raucher, S. (6) 287 Raut, S.V. (1) 254; (7) 12 Rauzy, K. (1) 391; (4) 74 Rayner, B. (6) 102, 148, 149 Raytarskaya, M.V. (5) 143 Razhabov, A. (5) 101 Reddy, C.D. (5) 13 Reddy, D. (8) 155 Reddy, K.S.(6) 249, 253 Redrnore, D. (5) 68, 203 Reed, A.E. (2) 4 Reed, R.A. (8)264 Rees, C.W. (4) 9; (5) 195, 196 Reese, C.B. (6) 4, 90 Regan, W . (6) 101 Regitz, M. (1) 6, 204, 331, 334, 374 Reid, L.S. (6) 141 Reid, S.S. (6) 314 Reidalova, L.1. (8) 97 Reilly-Gauvin, K. (5) 222 Rein, T. (7) 57 Reitel, G.V. (1) 345-347; (4) 67, 69, 75 Rerniszewsk, S.W. (7) 98
0rganoph osph orus Chemistry Rengen, K. (1) 223, 224 Renhowe, P.A. ( I ) 226; (7) 20 Renneberg, H. (1) 352; (4) 66 Renner, G. (8) 198 Resvick, R. (6) 45 Reuter, J. (1) 41 Revenko, G.P.(1) 103 Rhee, Y . 4 . (6) 163 Rheingold, A.L. (8) 93 Ricard, L. (1) 304, 305, 378, 383, 399, 401, 403 Ricca, G. (5) 136; (8) 161 Rich, A . (6) 240 Rich, L.C. (5) 186 Richman, D.D. (6) 16 Richter, W . (4) 31, 32; (5) 102, 103 Rickard, C.E.F. (1) 218, 351 Rida, S.M. (8) 95 Rideout, D. (3) 6; (4) 6 Rider, P. (6) 91 Riding, G.H.(8) 101, 268 Ried, W . (1) 415; (8) 193 Riedl, T. (1) 407 Riendeau, D. (7) 87 Riesel, L. (8) 24 Rietzel, M. (8) 85, 202, 203 Rima, G. (5) 135 Risser, S.M. (8) 11, 12, 247 Robert-Guroff, M. (6) 113 Roberts, N.K. (1) 23; (5) 287 Roberts, S.M. (6) 48, 49 Robertson, D.L. (6) 242 Robertson, S.A. (6) 95 Robic, N. (6) 292 Robins, A.M. (7) 79 Robins, M.J. (6) 45 Robinson, D.H. (4) 3; (5) 120 Robinson, W.T.(7) 11 Robl, J.A. (5) 115 Robles, J . (6) 63 Rockenbauer, A. ( I ) 190 Rockensuss, W . (1) 58 Roder, T. (7) 15 Rodger, A.J. (6) 310 Rodi, Y.K. ( I ) 344, 397; (4) 76; (8) 191 Rodrigo, M.M. (8) 271 Rodriguez, M. (7) 123, 124 Roe, D.C. (1) 136 Roelen, H.C.P.F. (4) 45 Riiling, A. (6) 47 Riischenthaler, G.-V. (1) 142, 21 1; (5) 150; (8) 34, 35, 41 Roesky, H.W. (7) 30; (8) 21, 33, 85, 88-90, 189, 202-204 Roesky, M. (1) 58 Rogers, K.L.(5) 183
Rogers, M. (5) 266 Rohrbaugh, D.K. (5) 91, 288 Rohse, S. (5) 57, 238 Rohwer, H.E. (3) 36 Roig, A. (8) 270 Rokach, J. (7) 87 Rokita, S.E. (6) 191 Rolsrna, P.B. (8) 287 Rornanenko, E.A. (1) 216 Rornanenko, V.D. (1) 279, 281, 292, 342, 345-347; (4) 67-69, 73, 75; (8) 17, 30 Rornanov, G.V. (1) 105 Roobeek, C.F. (1) 173 Roper, W.R. (1) 218, 351 Rose, W.C. (6) 33 Roserneyer, H. (6) 139 Rosenbach, M.T. (6) 7 Rosenberg, I. (6) 21-23, 26 Rossetto, G. (1) 59 Rossi, J.-C. (7) 83 Rossi, R.A. (1) 63, 64 Rostinejad, F. (6) 67 Rougee, M. (6) 214 Rouillard, M. (7) 66 Roundhill, D.M. (4) 23 Roundhill, M.D. (1) 127 Rowley, S.P. (1) 171 Royan, B.W. (1) 364; (4) 72 Rozanov, I.A. (8) 188, 297 Rozinov, V.G. (5) 109, 110; (8) 40, 196 Ruban, A.V. (1) 279, 345-347; (4) 67-69, 75; (8) 17, 30 Rudavskii, V.P. (8) 76, 96 Rudinskaya, G.Ya. (8) 256 Rudolph, L.N. (6) 147 Rudornino, M.V. (1) 129; (5) 143 Rudzevich, V.L. (8) 205, 298 Ruf, K. (6) 136 Ruffner, D.E. (6) 230, 236 Rufinska, A. (1) 335 Ruiz, J. (1) 53 Ruiz-Montez, J. (5) 206 Runova, O.B. (5) 32 Rusinskaya, G.Ya. (8) 255 Russell, D.R. (1) 128; (3) 34 Russell, M.J.H. (3) 3 Russo, G. (7) 59 Rutkovskii, E.K. (2) 30 Rutt, J.S. (8) 118, 133, 219, 243 Rybasova, G.I. (8) 225, 226 Ryono, D.E. (5) 222 Ryschkewitsch, G.E. (8) 91 Ryu, E.K. (1) 146 Ryurntsev, E.I. (8) 272 Ryzhikova, T.Ya. (1) 105
377
Author Index Saadein, M.R. (5) 305 Saak, W. (1) 210 Saasaki, J. (8) 56 Sabol, J.S. (7) 82 Sadana, K.L. (6) 167 Sadanani, N.D. (5) 77 Sadkova, D.N. (5) 236 Sadovskaya, N.P. (8) 96 Safadi, M. (5) 176, 218, 274 Safina, Yu.G. (2) 12; (5) 187 Safsaf, A. (5) 297 St.Clair, T.L. (8) 131 Saito, 1. (3) 23; (6) 171, 254, 255, 273 Saito, M. (1) 161 Saito, R. ( 5 ) 60 Saito, S . (6) 29 Sakata, T. (6) 218, 231 Sakatsume, 0. (6) 92 Saki, N. (8) 288 Salamonczyk, G.M. (6) 37 Salem, S.M. (7) 101; (8) 53 Salim, A. (1) 160 Sal’keeva, L.K. (4) 1 1 Salmon, L. (6) 292 Salz, E. (8) 270, 271 Samano, V. (6) 45 Samarai, L.I. (5) 226 Sammakia, T. (7) 94 Sample, K.R. (6) 169 Samuels, W.D. (8) 248 Samuelsson, B. (1) 215 Sancar, A. (6) 177, 178 Sanchez, M. (1) 281, 369, 370, 391; (4) 70, 71, 73, 74 Sanders, M. (5) 89 Sandstrom, A. (6) 245 Sano, H. (8) 106 Santa, H. (6) 11 Santacroce, C. (6) 182 SantaLucia, J., jun. (6) 179, 180 Santarsiero, B.D. (2) 32 Santo, K. (8) 56 Sapino, C. (1) 172 Sardina, F.J. (3) 24 Sarfati, S.R. (6) 205 Sargent, M.V. (1) 225 Sarina, T.V. (1) 279 Sarvarova, N.N. (1) 139 Sasagawa, K. (8) 98 Sasaki, K. (6) 44 Sasaki, M. (3) 10 Sasaki, T. (6) 89 Sasaki, Y. (3) 7 Sasakurd, T. (8) 177, 178 Sasmor, H. (6) 125 Satge, J. ( 5 ) 135 Sathyanarayana, S . (6) 202
Sato, E. (6) 207 Sato, H. (4) 54 Sato, R. (1) 161 Sam, T. (1) 310 Sattelberger, A.P. (1) 10 Sattler, G. (1) 169 Sauer, W. (1) 402 Savage, G.P. (7) 114 Savati, L. (8) 240 Savenkov, N.F. (5) 252 Savignac, P. (1) 115, 326; (5) 113, 132, 244; (7) 56, 83 Sawada, N. (6) 288 Saxe, J.D.(6) 128 Sayadyan, S.V. (1) 65, 94 Scaringe, S.A. (6) 83 Scarlato, G.R. (7) 21 Schabtach, E. (6) 333 Schacht, E. (8) 234, 292 Schadler, H.D. ( I ) 32, 377 Schaefer, H.F., 111 (8) 103 Schaefer, M.A. (8) 208 Scheer, M. (1) 32 Scheide, G.M. (8) 4 Schell, R. (6) 10 Schilz, J. (5) 7 Schimmel, P. (6) 300 Schinazi, R.F. (6) 50 Schippel, 0. (7) 33 Schlewer, G. ( 5 ) 32 Schleyer, P.von R. (2) 4 Schlosser, M. (7) 4 Schlossman, A. (5) 274 Schmid, B. (1) 133 Schmid, R. (1) 107 Schmidbaur, H . (1) 81, 164, 165, 229; (8) 16 Schmidpeter, A. (1) 366, 379, 390; (7) 7 Schmidt, G . (6) 17 Schmidt, H. (1) 31, 333, 377 Schmidt, H.G. (8) 88, 202 Schmidt, J. (7) 74 Schmidt, K.R. (7) 73 Schmutzler, R. (1) 198, 202; (2) 9, 19; (5) 240; (8) 87 Schnalke, M. (1) 46, 47 Schneider, H.-W. (1) 40, 42 Schneider, K.C. (6) 133 Schneider, R. (1) 204 Schnell, M. (5) 149 Schnick, W. (8) 223 Schoeller, W.W. (1) 294, 317, 340, 341 Schoenen, F.J. (6) 263 Schonholzer, P. (1) 107 Scholz, G . (1) 48 Schrader, S. (1) 264; (8) 18
Schrader, T. (5) 204 Schreiber, S.L. (6) 76, 263, 265, 267; (7) 94 Schriver, M.J. ( I ) 350; (8) 13 Schroder, H.C.(6) 138 Schrumpf, F. (8) 89 Schubert, F. (6) 187 Schulte, G.K. (7) 118 Schulten, M. (1) 201 Schultz, C. (4) 44; (5) 27 Schultz, P. (6) 219 Schultz, P.G.(6) 95, 96 Schulz, J. (5) 6 Schulz, M. (7) 33 Schumann, H.(1) 269, 270 Schuster, H. (1) 338 Schwalbe, C.H.(5) 182; (6) 25 Schwartz, J . (6) 119 Schwartz, 0. (6) 13 Schwartz, U.M. (7) 1 1 1 Schwartzman, M.L. (7) 86 Schwerdtfeger, P. (1) 351 Sciavovelli, 0. (4) 8 Scilimati, A . (4) 8 Scott, L.T. (1) 15 Scott, S.A. (6) 213 Searle, M.S. (6) 274 Sebastian, M. (1) 113 Seega, J . (5) 151 Seela, F. (6) 47, 126, 127, 139, 173, 175 Seernan, N.C. (6) 221, 222 Seewald, M.J. (5) 38, 39 Segall, Y. (5) 89 Sekine, M. (6) 3, 93 Sekine, S. (8) 106 Sekiya, K. (6) 29 Selvaraj, 1.1. (8) 155 Semakov, A.V. (8) 253 Semenenko, N.M. (1) 280 Semenii, V.Ya. (5) 111 Senaldi, A. (7) 59 Senyukh, S.M. (5) 159 Sepulchre, C. (3) 4; (7) 88 Sera, T. (6) 254 Seratinowska, H.T. (6) 90 Seredkina, S.G. ( 5 ) 108 Sergent, M. (4) 64 Serianni, A.S. (6) 150 Setzer, W.N. (5) 302, 304, 305 Shablovskaya, E.A. (8) 76, 96 Shagidullin, R.R. (5) 290 Shagi-Mukhametova, N.M. (2) 22 Shagvaleev, F.Sh. (1) 217 Shaikhudinova, S.I. (1) 92 Shakirov, I.Kh. (5) 290 Shamselvaleev, F.M. (5) 98; (8)
378 39 Shankland, P . (6) 125 Shapiro, G. (7) 121 Sharma, P. (6) 202 Sharp, T . R . (8) 107, 108 Shashidhar, M . S . (5) 137 Shatzmiller, S. (5) 193 Shaw, A . A . (6) 335 Shaw, A.R. (6) 195 Shaw, B . L . ( I ) 19 Shaw, G. (4) 21 Shaw, L . S . (8) 146 Shaw, R . A . (8) 126, 143-146 Shawali, A . S . (8) 68 Shcherhina, T . M . (5) 129; (8) 78 Shea, R.G. (6) 192 Sheidecker, S. (8) 123 Sheldrick, G . M . (7) 30; (8) 21, 90, 202 Shen, G.S. (1) 138; (7) 24 Shen, T . Y . (4) 43; (5) 29 Shen, Y. ( I ) 257, 258; (7) 23, 42, 43, 45 Shenoy, S.J. (5) 66, 99 Shephard, W . B . (1) 218 Sherman, A . S . (8) 17 Shermolovich, Yu.G. (1) 67; (5) 112 Sheu, J.-H. (7) 77 Shevchenko, I . V . ( I ) 137 Shi, G. (8) 26 Shi, M. (5) 281, 282 Shi, Y. (8) 135 Shihaev, V . P . (8) 230 Shihutani, S. (6) 156 Shiganakova, O . V . (1) 102 Shigematsu, H. (8) 154 Shigenematsu, H. (8) 228 Shimada, T. (6) 113 Shin, J . (3) 6; (4) 6 Shinde, B.R. (5) 66, 99 Shinohara, T. (5) 33 Shinozuka, Z. (6) I13 Shiornoto, K. (8) 239 Shiozawa, N. (8) 71 Shiro, M. (5) 229 Shoner, S . C . ( I ) 355 Shriver, D . F . (8) 264 Shtennikova, I . N . (8) 272 Shudo, K. (6) 140 Shue, Y.-K. (7) 19 Shuker, A.J. (7) 117 Shumeiko, A . E . (8) 1 1 1 Shvets, V.I. (5) 32 Sibi, M.P. ( I ) 226; (7) 18, 20 Siedlecki, J.M. (6) 176 Sigurdsson, S.T. (6) 287 Silherzahn, J . (7) 13
Organophosphorus Chemistry Simonov, Yu.A. (8) 298 Simpkins, L.M. (5) 115 Simurova, N.V. (5) 145, 146 Sinden, R.R. (6) 200 Sinegovskaya, L.M. ( I ) 159 Singh. C . (6) 128 Singh, J.D. (5) 56 Singh, U . ( I ) 163 Singler, R.E. (8) 210, 229, 231 Singman, C . N . (6) 62 Sinitsa, A . D . (2) 31; (4) 33, 34; (5) 93, 145-148, 254, 255; (8) 77, 97 Sinou, D . ( I ) 186 Sinyashina, T . N . (2) 14 Siriwardane, U. (4) 24 Sitdikova, T.Sh. ( I ) 217 Siv, P.G.C. (4) 64 Sivolobova, O.A. (5) 152 Skelton, B.W. (1) 106; (3) 12 Sklenar, V . (6) 319 Skoblikova, L.I. (5) 252 Skokotas, G. (6) 266 Skolimowski, J . J . ( I ) 413 Skowronska, A . (5) 156, 261 Skowronski, R. ( I ) 259 Skrzypczynski, Z. (6) 105 Skuratovich, L.G. (8) 119 Skvorcov, S. ( I ) 97 Sladky, F. (1) 246; (5) 237 Slata, J.M. (5) 234 Slavin, L.L. (6) 306 Sleath, P.R. (6) 58 Slim, G . (6) 234 Smalley, R.K. (7) 101; (8) 53 Smeets, W.J.J. (1) 414 Smirnova, L.V. (5) 257 Smirnova, V . N . (8) 273 Smith, A , (5) 275 Smith, A . B . , 111 (7) 98 Smith, A . L . (6) 262, 264 Smith, C . A . (6) 154 Smith, C . D . (3) 16 Smith, D . B . (7) 94 Smith, E.C.R. (5) 219 Smith, J . D . (1) 179 Smith, M.B. (1) 98 Snyder, J.R. (6) 150 Snyder, S.H.(5) 34 Soares, V . M . (5) 88 Sohol, R.W. (6) 107, 138 Sofia, M.J. (5) 115 Sokol, V.I. (8) 297 Sokolov, M.P. (5) 264 Sokolov, V.B. (1) 212, 213; (5) 8, 188, 303 Soliman, F.M. (7) 28 Soliman, F.S.G. (8) 95
Solodenko, V . A . (5) 190, 208, 209 Solov’ev, A . V . (1) 67 Solov’eva, L . D . (1) 150 Sonawane, H . R . ( I ) 148 Sonveaux, E . (6) 152 Sood, M. (8) 31 Soroka, M . (5) 197 Soto, K. (3) 17 Sournies, F. (8) 113, 122-125 Southgate, R . (7) 79 Sowers, L . C . (6) 326 Spahn, M. (1) 417; (8) 194 Spangler, C . W . (7) 61; (8) 135 Sparkes, M.J. (5) 175, 183 Speier, G. (8) 25 Spek, A . L . (1) 414 Spencer, J.T. (1) 298 Spiess, B. (5) 32 Spiess, E. (6) 66 Spindler, C . ( I ) 390 Sproat, B.S. (4) 51; (6) 91, 143, 144, 197 Squier, C . A . (4) 30 Srivastava, D . K . (1) 11 Srivastava, G. (5) 55 Srivastava, P . C . (8) 23 Srivastava, S . K . (5) 56 Srivastava, T.N. (5) 56 Stadler, B . (4) 44 Stadler, C. (5) 27 Stalke, D. ( I ) 30, 341; (8) 21 Stam, C . H . (8) 92, 200 Stamrnler, H.-G.( I ) 31 1 Stand, E . A . (6) 157 Stang, P.J. ( I ) 234 Stangier, P. (6) 42 Stapleton, A . (7) 117 Stec, W.J. (5) 61, 95; (6) 37, 106, 1 1 1 Steenhergen, A . (8) 151 Steglich, W. (5) 204 Steier, W.H.(8) 135 Steigelmann, 0. ( I ) 81 Stein, C . A . (6) 106, 112, 113 Stelzer, 0. (1) 208; (8) 87 Stemerick, D . M . (3) 5; (7) 60 Stepanchuk, V . A . (8) 96 Stepanov, A . E . (5) 32 Stepanov. B.I. ( I ) 124 Stepanova, Yu.Z. ( I ) 342 Stephan. M. ( I ) 118; (4) 4, 36 Stepura, G.S. (8) 97 Stern, M.K. (4) 53; (6) 246 Stetten, E. (6) 316 Stezowski, J . J . (6) 155; (7) 74 Stille, J.K. (1) 199 Stiller, R. (6) 41
Author Index Stoelben, S. (7) 107; (8) 44 Stokes, J.P. (3) 26 Stoll, K. (1) 34 Stoller, A. (3) 4; (7) 88 Stone, F.G.A. (1) 307 Stoner, M.R. (5) 84 Storer, R. (6) 48, 49 Storhoff, B.N. (1) 100 Storm, C. (6) 11 1 Stout, T.J. (6) 263, 265 Stowell, M.H.B. (5) I17 Straubinger, R. (6) 118 Straw, T.A. (2) 7 Streitwieser, A. (2) 4 Strekas, T.C. (6) 31 1 Streubel, R. (1) 207; (8) 28 Stroehl, D. (5) 52 Struchkov, Yu.T. (1) 28, 102, 175, 265; (5) 299 Struszczyk, H. (8) 141, 182 Stubhe, J. (6) 45, 46, 247, 256, 258, 259 Studnicka, A . (8) 184 Stutzer, A . (1) 165 Stuhmiller, L.M. (6) 16 Stuke, M. (1) 58 Sturnpf, R. (4) 46; (5) 43 Suades, J. (1) 177 Subasinghe, C. (6) 106 Suda, K. (1) 240, 241; (7) 8 Suda, S. (1) 262 Sudhakar, P.V. (7) 3; (8) 8 Suetke, T. (8) 179 Suehiro, N. (6) 334 Suemune, H. (6) 266 Sueptitz, G. (6) 94 Sugai, S. (7) 112 Sugiyarna, H. (6) 171, 254, 273 Suhadolnik, R.J. (6) 107, 138 Sukhozhenko, 1.1. (5) 2 Sulga. J. (8) 249 Sullivan, A.D. (8) 229 Sulston, I. (6) 91 Sundell, M. (5) 131 Sunthankar, P.S. (5) 13 Suppel’, 1.Ya. (5) 258 Surpina, M.Ya. (8) 183 Sutton, B.M. (1) 16 Suvalova, E . A . (5) 93 Suzuki, H. ( I ) 263; (7) 16 Suzuki, S. (1) 267 Suzuki, Y. (4) 54, 55; (6) 70 Svedas, V . K . (5) 208 Swarny, K.C.K. (2) 1, 5, 6, 20 Swann, P.F. (6) 165 Swenton, L. (7) 89 Symons, M.C.R. (8) 202, 203 Szafraniec, L.L. (5) 91, 288
379 Szameitat, J. (1) 307 Szantay, C.S. (7) 76 Szczesny, Z. ( 5 ) 197 Szeja, W. (5) 49 Szrnuszkovic, J. (4) 14 Szoelloesy, A. (1) 400; (3) 13 Szoka, F.C., jun. (6) 118 Szostak, J.W. (6) 240, 241, 243, 299 Tabor, A.B. (6) 267 Tachon, C. (1) 284 Tada, M. (8) 59 Tada, N. (1) 250 Tada, Y. (8) 138, 237, 275-279 Taira, K. (6) 328, 331 Takagi, M. (6) 275, 281, 282 Takahashi, K. (8) 114-116, 180 Takahashi, T. (5) 229 Takaka, H. (6) 70 Takaki, M. (6) 92 Takaku, H. (4) 54, 55; (6) 92 Takarnuku, S. (5) 10, 278-282 Takanarni, T. (1) 240, 241; (7) 8 Takashirna, H. (6) 29 Takaya, H. (1) 5, 17, 108 Takaya, Y. (1) 168 Takeishi, M. (8) 71 Takenaka, S. (6) 275, 281, 282 Tdkeuchi, H. (1) 233; (4) 13 Takeuchi, 1. (5) 300 Tamai, Y. (5) 83 Tamura, M. (6) 303 Tan, W.H.W. (5) 243 Tanabe, K. (6) 331 Tanaka, H. (6) 29 Tanaka, T. (6) 218, 231 Tanaka, Y. (1) 233 Tang, J.-S. (5) 67 Tang, J.-Y. (6) 85, 204 Tanigaki, T. (8) 137, 157 Taniguchi, M . (8) 276 Tanimura, H. (6) 87, 88 Tankard, M. (7) 58 Tanswell, J.L. (1) 23; (5) 287 Tapley, C.L. (1) 100 Taran, V . V . (8) 76 Tarasova, R.I. (1) 217; (8) 190 Tarazona, M.P. (8) 270, 271 Tarraga, A. (8) 51 Tasz, M.K. (1) 259 Tatdrinova, A . A . ( I ) 159 Tattershall, B.W. (4) 81 Taylor, G. ( 5 ) 266; (6) 53, 54 Taylor, N.J. (1) 126 Tebbe, K.-F. (1) 49 Tebby, J.C.(7) 9
Teichmann, H. (5) 6, 7 ten Wolde, A. (3) 30 Thule, R. (4) 59; (6) 84, 151 Terent’eva, S.A. (2) 24 Terlouw, J.K. (1) 352; (4) 66 Teulade, M.-P. (5) 132 Texier, F . (7) 64 Thal, C. (7) 103 Thatcher, G.R.J. (5) 164, 267 Thea, S. (5) 270 Theisen, P. (6) 66 Thelnalt, U. (8) 147 Thenappan, A. (7) 71 Therbert, A.B. (5) 34 Thiele, M. (1) 379; (7) 7 Thiele, R. (1) 294 Thiern, J. (6) 41, 42, 43 Thiesen, H.J. (6) 297 Thimm, J. (6) 43 Thomas, E.J. (7) 97 Thompson, E.A. (6) 90 Thompson, W.J. (5) 15 Thomson, W. (6) 25 Thorimhen, S. (5) 206 Thornton, J.J. (6) 78 Thornton-Pett, M. (1) 95 Thuong, N.T. (4) 60; (6) 110, 190, 201, 209 Tilichenko, M.N. (1) 104 Tillett, J.G. (1) 160 Timokhin, B.V. (1) 220 Tinker, A. (4) 3; (5) 120 Tinoco, I., jun. (6) 217, 224, 225 Tiripicchio, A. (7) 31 Titskii, G.D. (8) 11 1 Tkachenko, S.E. (3) 14 Tocher, D . A . (8) 94 Toeke, L. (1) 400 Togni, A. (1) 134 Tohamy, F.A. (1) 144 Toia, R.F. (5) 89, 90 Toke, L. (3) 13 Tolrnachev, A.A. (1) 130 Tomcufcik, A.S. (8) 27 Tomioka, H. ( 5 ) 272 Tomohiro, T. (1) 162 Tomoi, M. (1) 238 Tondelli, L. (6) 324 Tonge, J.S. (8) 264 Tonnard, F. (1) 297 Topolski, M. (5) 199 Tordo, P. (1) 12; (5) 215 Torgasheva, N.A. (5) 46 Torgomyan, A . M . (5) 87 Torreilles, E. (7) 48; (8) 66, 67, 83 Tortora, P. (7) 59
Organophosphorus Chemistry
380 Toth, 1. ( I ) 89 Toto, S.D. (1) 110 Townsend, C.A. (6) 267 Toyota, K. (1) 277, 309, 310, 3 12-315 Trabelsi, H. (8) 37 Trapp, M.A. (8) 250 Trehearne, T.E. (1) 100 Trent, J. (7) 11 Trigo Passos, B.F. (1) 308, 348 Trishin, Yu.G. (1) 181; (5) 17, 158, 159 Trivedi, A. (8) 23 Trofimov, B.A. ( I ) 92, 93, 159 True, S. (8) 143, 144 Truesdale, L.K. (5) 82 Trzeciak, A. (5) 25 Tsai, B.D.(8) 130, 132 Tsao, C.-L. (1) 83 Ts’O, P.O.P. (6) 208 Tsunetsugu, S. (6) 44 Tsutsarin, V.V. (8) 76 Tsutsumi, Y. (6) 171 Tsvetkov, E.N.(1) 129; (3) 14; (5) 143, 295, 296 Tuck, D.G. ( I ) 29 Tuerk, C. (6) 298 Tufano, M.D. (7) 19 Tugnolli, V. (6) 324 Tuinman, R.J. (5) 138 Tuli, D.K. (6) 174 Tumanyan, V.G. (6) 277 Tunney, S.E. (1) 199 Tupchienko, S.K. (2) 31; (8) 77 Tur, D.R. (8) 230, 253, 255-258, 272, 273 Turdybekov, K.M. (5) 299 Turner, D.H. (6) 179, 180 Turner, M.L. (8) 149 Tuzhikov, 0.1. (1) 112 Tzschach, A. (5) 298 Ubusawa, M. (6) 29 Uchida, T. (1) 382 Uchida, Y. (1) 168, 250 Uchimaru, T. (6) 331 Uebayasi, M. (6) 328 Uehling, D.E. (7) 94 Ueland, J.M. (5) 117 Ueno, Y. (5) 60 Uesugi, S. (6) 218, 231 Ugi, 1. (4) 31, 32; (5) 102, 103 Uhl, G. (1) 333 Uhl, W. (1) 333 Uhlenbeck, O.C. (6) 172, 229, 230, 236 Uhlig, F. ( I ) 32
Uhlig, W. (1) 131 Ulbrich, R. (5) 276 Umeda, M. (8) 99 Umezu, Y. (3) 7 Unno, M. (1) 15 Urata, H. (6) 303 Usha, K. (2) 28; (8) 31 Usman, N. (6) 83, 237, 240 Ustenko, S.N.(4) 20 Uzanski, B. (6) 111 Uziel, J. (5) 206 Vaahs, T. (1) 35, 39 Vaal, M.J. (1) 155 Vacca, J.P. (5) 36 Vahldiek, M. (1) 113 Vahrenkamp, H. (7) 31 Valentine, K.G.(6) 268 Valerig, R.M. (5) 23 Valitskii, Y.V. (4) 33 Valu, K.K. (6) 283 Van Aerschot, A. (6) 18, 19 van Atta, R.B. (6) 252 van Boeckel, C.A.A. (5) 30, 31; (6) 65, 132 van Bolhuis, F. (8) 150 van Boom, J.H. (4) 45; (5) 138; (6) 59, 104, 193, 215, 251 Vanbrecht, B.J.A.M. (3) 36 Van Dam, E.M.A. (6) 193 van de Grampel, J.C. (8) 129, 150, 151, 187 van den Elst, H. (4) 45; (6) 193 van den Winkel, Y. (1) 337, 414 van der Bosch, H. (6) 16 van der Does, T. (1) 414 van der Gen, A. (3) 29, 30; (6) 59 Van der Haest, A.D. (5) 79, 80 Van der Heijden, H. (1) 185 van der Laarse, J. (1) 414 van der Lee, A. (8) 187 van der Marel, G.A. (4) 45; (5) 138; (6) 59, 104, 193, 215, 25 1 Vanderveer, D.G. (5) 302 van de Ven, F.J.M. (6) 215 Van Doorn, J.A. (1) 185 Van Engen, D. (1) 121, 122 van Es, J.J.G.S. (3) 29, 30 van Genderen, M.H.P. (6) 226 van Leeuwen, P.W.N.M. (1) 173 Vannoorenberghe, Y. (2) 25 van Oort, A.B. ( I ) 22 Vanquickenborne, L.G. ( I ) 363 Vansweevelt, H. (1) 363
Vapirov, V.V. (8) 111 Varani, G. (6) 217 Varmus, H.E. (6) 116 Vasella, A. (5) 139 Vasil’eva, N.V. (8) 255, 273 Vasisht, S.K. (8) 31 Vasser, M. (6) 74 Vasseur, J.-J. (6) 149 Vasyanina, L.K. (4) 38 Vavcikova, K. (5) 74 Vedachalam, M. (5) 155 Veith, M. (1) 195; (8) 156 Veits, Yu.A. (1) 68, 69, 280 Velikokhat’ko, T.N. (8) 86 Verchkre-Bkaur, C. (6) 292 Verdine, A.M. (6) 158 Verdine, G.L. (6) 76, 159, 160 Verkade, J.G. (4) 27; (5) 18 Verkruijsse, H.D. (1) 21 Verma, P.K. (8) 31 Vidal, A. (7) 102; (8) 49 Vidal, M. (1) 228; (3) 11 Viktorov-Nabokov, O.V. (8) 96 Vilaplana, M.J. (7) 108; (8) 46, 50 Villafranca, J.J. (6) 6 Vina, S. (1) 253 Vinader, M.V. (8) 15, 43, 55 Vinayak, R. (6) 66 Vincens, M. (1) 228; (3) 11 Vincze, A. (5) 218 Virgil, S.C. (7) 32 Visscher, K.B. (8) 235, 246 Visser, H.C. (1) 352; (4) 66 Vitola, A. (8) 249 Vittadini, A. (1) 59 Vogtle, F. (7) 99 Volkmann, M. (7) 99 Volodin, A.A. (8) 218 Volpin, M.E. (1) 175 Volwerk, J.J. (5) 137 von der Gtinna, V. (1) 360; (8) 29 von Itzstein, M. (I) 152 Vonka, V. (6) 23 von Kiedrowski, G. (6) 146 Von Schneering, H.G. (1) 42, 71 Vo-Quang, L. (5) 198 Voronkov, M.G. (1) 92, 93, 159 Vostrowsky, 0. (7) 75 Votruba, I. (6) 22, 23, 24 Vu, C.B. (7) 39 Vu, H. (4) 18; (6) 66, 103 Vukojevic, N.S. (5) 293 Vul’fson, S.G.(1) 139 Vymenits, A.B. (1) 175 Vysotskii, V.I. (1) 104
Author index Wada, M. (1) 255 Wada, T . (4) 56-58; (6) 71, 72, 122 Waegell, B. (1) 109 Waggoner, K.M. (1) 55, 355 Wagner, E. (5) 20 Wagner, I. (1) 210 Wagner, 0. (1) 331 WaiTan, W.H.-L. (1) 409, 410 Wakelin, L . P . G . (6) 279, 283, 284, 309 Wakselman, M. (4) 4 Walder, J . A . (6) 134 Walker, D . A . (6) 97 Walker, R.T. (6) 12, 29 Walker, S. (6) 268 Wallen, C . A . (6) 15 Walter, A. (1) 101 Walton, D . R . M . (I) 323 Walton, T.J. (6) 327 Walz, L. (1) 71 Wamhoff, H . (7) 107; (8) 44, 48 Wang. C. ( 5 ) 106; (6) 162 Wang, C.-K.(6) 262 Wang, M.F.(4) 3; (5) 120 Wang, M.L. (8) 109, 110 Wang, P. (2) 4 Wang, R.-J. (1) 25 Wang. S.N. (6) 249 Wang, T. (7) 42, 43; (8) 208 Wang, W. (4) 14 Wang, Y. (6) 221 Wang, Y.-S. (6) 321 Waring, M.A. (5) 72 Warren, S. (3) 19 Wasiak, J. (6) 105 Wassef, N.W. (1) 144 Wassermann, H . H . (7) 39 Wasylishen, R.E. (1) 350; (8) 13 Watanahe, F. (7) 90 Watanahe, M . (5) 69, 272 Watanabe, Y. (5) 33 Watkins, C.L. (1) 11 Watt, D . S . (7) 91 Watts, D . (5) 266 Wawer, A. (1) 196 Wawer, 1. (1) 196 Weber, L. (1) 269-272, 306, 31 1 Webster, H.F. (3) 16 Weidner, M.F. (6) 287 Weiguo, C. (7) 44 Weik, C. (5) 193 Weiler, B.E. (6) 138 Weintraub, P.M. (7) 82 Weiyu, D . (7) 44 Welch, S.C. (5) 70 Wells, R.L. (2) 10 Welz, U . (1) 317
381 Wen, M.-X. (5) 141 Wendehorn, S . V . (6) 262, 264 Wender, P . A . (6) 261 Wenkert, E. (7) 77 Werner, H. (1) 71; (7) 33 Werner, S. (7) 41 Werner, W. (8) 22 Wessolowski, H. (5) 150 West, A.P. (1) 121, 122 West, S . D . (1) 100 Westerduin, P. (5) 30, 31 Westermann, H. ( I ) 70; (4) I 7 Westmoreland, D . L . (1) 368; (5) 24 1 Westwood, R. (7) 101; (8) 53 Wettling, T. (1) 204, 334 White, A.H. (1) 106; (3) 12 White, J.D. (7) 6 White, P.S. (1) 364; (4) 72 Whitesides, G.M. (1) 125 Whittle, R.R. (8) 80 Wiaterek, C. (1) 46 Wiberg, N. (1) 338 Wickham, G. (6) 309 Widhalm, M. (1) 78 Wieber, M. (1) 198; (5) 57, 238 Wieczorek, M.W. (1) 227 Wiel, A. ( I ) 169 Wightman, J.P. (3) I 6 Wightman, R.H. (5) 212 Wijata, A. (5) 64 Wijmenga, S.S. (6) 257 Wilbrandt, D. (5) 6 Wild, S.B. (1) 123, 187 Wilke, E. (5) 151 Willens, H . A . M . (5) 30, 31 Williams, A. (5) 72 Williams, D.J. (5) 285 Williams, D . M . (6) 173-175 Williams, I.D. (1) 126 Willingham, R.A. (8) 210, 231 Willis, A.C. (1) 24 Willis, M.C. (6) 172 Wills, A.R. (1) 82 Wilson, G.E. (6) 322 Wilson, S . H . (6) 112 Wilson, S.R. (1) 91; (7) 52; (8) 19 Wilson, W.R. (6) 283, 285 Wimmer, T. (1) 164 Windscheif, P.-M. (7) 99 Wingfield, P. (6) 195 Wink, D.J. (4) 22 Winkeler, K.A. (4) 53; (6) 246 Winkler, T. (5) 253 Winter, R. (5) 150 Wintergrass, D.J. (4) 27; (5) 18 Wintersgill, M.C.(8) 266
Wintersohl, H. (7) 107; (8) 44 Winwood, D . (5) 5 Wise, W.B. (6) 169 Wisian-Nielson, P. (8) 208, 209, 250 Wisniewski, W. (3) 31 Withka, J . (6) 247 Witt, M. (8) 21 Wlotzka, B. (6) 146 Woenckhaus, C. (6) 206 Wojna-Tadeusiak, E. (5) 92 Wolf, J . (7) 33 Wolf, R. (1) 369, 370; (4) 70, 71 Wolfsberger, W. (1) 3, 84, 99, 132, 205; (8) 16 Wolmershauser, G. (1) 334 Wong, C.-H.(4) 42; (5) 19 Wong-Staal, F. (6) 113 Woo, J . (6) 287 Wood, C . E . (8) 4 Wood, G.L. (1) 167 Woodgate, P . D . (6) 283, 284 Woolins, J.D. (5) 285 Wooster, T.T. (8) 264 Worth, L., jun. (6) 258, 259 Wright, W.B., jun. (8) 27 Wrighton, M.S. (8) 7 9 Wrobel, L. (7) 114 Wroblewski, A . (4) 27; (5) 18 WU, A.-H. (4) 77; (5) 180; (7) 72 Wu, H.S.(8) 109, 110 Wu, J.V. (6) 125 Wu, S.Y. (5) 89, 90 Wu, T. (6) 82 WU, X.-P. (5) 77, 273 Wyatt, J.R. (6) 224, 225 Wynberg, H. (5) 79, 80 Xiang, Y. (1) 257; (7) 45 Xiang, Y.-B. ( 5 ) 20 Xie, Y. (8) 103 Xu, Y. (6) 304 XU, Y.-Z. (6) 165 Yaguchi, A . (8) 164, 165, 167, 169, 173-175 Yamaguchi, K. (3) 2 3 Yamaguchi, M. (3) 7; (7) 70 Yamaji, N. (6) 36 Yamamoto, H. (5) 94 Yamamoto, K. (1) 79 Yamamoto, M. ( 5 ) 262 Yamamoto, S. (1) 233 Yamamoto, Y. (7) 67
382 Yamashita, D.S. (7) 118 Yamashita, M. (5) 177 Yamashita, Y. (8) 245 Yamovskaya, V.L. (5) 46 Yan, S. (5) 289 Yanada, R. (4) 10 Yanagida, S. (4) 13 Yang, J.-H. (6) 237 Yang, Y.-C. (5)288 Yang, Z.-Y. (5) 163 Yaniv, D.R.(8) 264 Yano, S. (8) 140 Yanovskii, A.I. (1) 28, 102, 175 Yaolvskaya, A.J. (1) 150 Yaouanc, J.-J. (2) 27 Yarerna, K. (6) 183, 184 Yashirna, E. (6) 334 Yashiro, T. (5) 300 Yasuda, S. (7) 96 Yasui, M. (7) 16 Yasui, S. (1) 188 Yasunami, M. (1) 330 Yasunami, S. (8) 280, 281 Yau, E. (4) 61; (6) 121, 125 Yazawa, N. (1) 263 Ye, M. (5) 289 Yee, A . (4) 22 Yoneda, F. (4) 10 Yoneda, R. (5) 107; (8) 56 Yoon, H.S. (8) 114-116, 180 Yoshida, Y. (1) 238, 263 Yoshifuji, M. (1) 277, 309, 310, 312-315, 330 Yoshikawa, K. (1) 90 Yoshikawa, M. (6) 207 Yoshirnura, H. (1) 277, 309, 313, 314 Yu, J.H. (2) 21 Yu, P.L. (6) 69
Organophosphorus Chemistry Yu, P.S. (6) 90 Yu, Y. (8) 26 Yu, Z. (6) 6 Yuan, Z. (1) 126 Yuki, Y. (1) 239 Yurchenko, R.I. (1) 112; (5) 53 Yurchenko, V.G. (5) 53 Yusupov, M.M. (5) 101 Zaharylo, S.V. (6) 61 Zabirov, N.G. (5) 98, 100; (8) 38, 39 Zagnibida, D.M. (8) 96 Zahra, J.-P. (1) 109 Zakharkin, L.I. (1) 28, 279 Zal’tsman, I.S. (2) 30, 31; (8) 77 Zarnecnik, P.C. (6) 203 Zanella, P. (1) 59 Zanin, B. (8) 123-125 Zanotto, L. (1) 179 Zarges, W. (7) 51 Zarrinrnayeh, H. (6) 80, 272 Zatorski, A. (7) 120 Zavlin, P.M. (5) 62 Zawadzki, S. (5) 64 Zayed, M.F. (7) 25 Zhigniew, J. (8) 121 Zbiral, E. (5) 167, 168 Zecchi, G. (7) 104; (8) 57 Zeelie, B. (3) 36 Zein, M. (6) 267 Zeiss, H.-J. (5) 179 Zellner, K. (1) 62; (7) 34 Zercher, C.K. (6) 261 Zettlmeier, W. (1) 117; (4) 65 Zhang, D. (1) 392 Zhang, G. (6) 62
Zhang, J. (5) 106 Zhang, J.-L. (1) 394 Zhang, L. (5) 106; (6) 40 Zhang, L.-J. (7) 29 Zhang, R. (5) 140, 157 Zhang, S. (1) 76 Zhang, W. (5) 29 Zhang, W.-S. (4) 43 Zhang, Y. (2) 4 Zhao, M. (5) 106 Zhao, Y. (5) 289; (8) 6 Zhao, Z. (7) 21 Zheng, J. (1) 392 Zherebtsov, A.A. (5) 109 Zhigareva, C.G. (1) 28 Zhou, L. (6) 157 Zhou, W. (5) 141 Zhou, X.-X. (6) 244 Zhou, Y. (7) 23 Zhu, N.J. (8) 44 Zhurinov, M.Kh. (5) 299 Zhut-skii, P.V. (2) 22; (5) 213 Zibuk, R. (7) 98 Ziegler, J. (1) 14 Ziegler, M.L. (1) 405 Ziller, J.W. (7) 32 Zilm, K.W. (1) 276 Zirnrnerling, R. (5) 52 Zimrnerrnan, J . (6) 276 Zinchenko, S.V. (5) 109 Zinn, A. (8) 294 Zon, G. (6) 75, 99, 106, 108, 113, 115, 118, 304, 305 Zotov, Yu.L. (1) 111 Zschunke, A . (1) 97 Zsolnai, L. (1) 266, 322 Zurmuhlen, F. (1) 204 Zwierzak, A. (8) 72 Zykova, T . V . (1) 217