Organophosphorus Chemistry (SPR Organophosphorus Chemistry (RSC)) (Vol 29)

Organophosphorus Chemistry Volume 29 A Specialist Periodical Report Organophosphorus Chemistry Volume 29 A Review of...

Author: D. W. Allen | J. C. Tebby

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Organophosphorus Chemistry Volume 29

A Specialist Periodical Report

Organophosphorus Chemistry Volume 29 A Review of the Literature Published between July 1996 and June 1997 Sen io r Reporter D. W. Allen, Sheffield Hallam University, Sheffield, UK J. C. Tebby, Staffordshire University, Stoke-on-Trent, UK Reporters

N. Bricklebank, Sheffield Hallam University, UK 0. Dahl, University of Copenhagen, Denmark J. A. Grasby, University of Sheffield, UK C . D. Hall, King's College, London, UK M. C. Salt, Staffordshire University, Stoke-on- Trent, UK R. N. Slinn, Nantwich, UK J. C. Van de Grampel, University of Groningen, The Netherlands B. J. Walker, The Queen's University of Belfast, UK D. M. Williams, University of Sheffield, UK

ROYAL SOCIETY OF CHEMISTRY

ISBN 0-85404-319-5 ISSN 0306-0713

0The Royal Society of Chemistry 1999 All rights reserved Apart from anyfair dealing for the purposes of research or private study, or criticism or review as permitted under the terms of the UK Copyright, Designs and Patents Act, 1988, this publication may not be reproduced, stored or transmitted, in any form or by any means, without the prior permission in writing of The Royal Society of Chemistry, or in the case of reprographic reproduction only in accordance with the terms of the licences issued by the Copyright Licencing Agency in the UK, or in accordance with the terms of the licences issued by the appropriate Reproduction Rights Organization outside the WK.Enquiries concerning reproduction outside the terms stated here should be sent to The Royal Society of Chemistry at the address printed on this page.

Published by The Royal Society of Chemistry, Thomas Graham House, Science Park, Milton Road, Cambridge CB4 OWF, UK For further information see our web site at www.rsc.org Typeset by Computape (Pickering) Ltd, Pickering, North Yorkshire, UK Printed by Athenaeum Press Ltd, Gateshead, Tyne and Wear, UK

Introduction

Following the retirements of long serving authors reported in the introduction to volume 28, we have to note futher changes to the team. After acting as Senior Reporter since volume 15, Brian Walker has now relinquished this role, which has been taken on by John Tebby. Happily, Brian continues as an author, now contributing the ‘Quinquevalent Phosphorus Acids’ chapter instead of the ‘Ylides and Related Compounds’ chapter which he has written since volume 13! We also have to note with regret that Otto Dahl has decided to retire from authorship of the ‘Tervalent Phosphorus Acid Derivatives’ chapter, having also contributed since volume 15. We thank Brian and Otto for sustained comprehensive and critical writing in these areas over many years. We are delighted to report that Terry Kee has agreed to take over Otto Dahl’s chapter in the next volume. Sadly, this will also be the final volume to which Jane Grasby and David Williams will contribute the ‘Nucleotides and Nucleic Acids’ chapter, and we thank them for their efforts over the last four years. On a brighter note, we welcome Neil Bricklebank as the new author of the ‘Ylides and Related Compounds’ chapter, J. C. Van der Grampel as the new author of the ‘Phosphazenes’ chapter, and also Mike Salt joins Robert Slinn as the co-author of the ‘Physical Methods’ chapter. Activity in the area covered by the ‘Phosphines and Phosphonium Salts’ chapter, which also covers the chemistry of low coordinate px bonded compounds, has continued at a high level, particularly with regard to the synthesis of new phosphines, although without major advances, doubtless reflecting the relative maturity of the area. Similarly, nothing of great note has emerged in the tervalent phosphorus acid derivatives area. The same, perhaps, could also be said of the area of ylide chemistry, although the application of phosphorus-based ylides in general synthetic chemistry continues unabated, and Warren’s group, in particular, has continued to develop the chemistry of phosphine oxide-based ylides. This year’s literature on nucleotide and nucleic acid chemistry has been dominated by interest in internucleoside linkages, and a number of novel approaches in this area have been described. In some cases, these have also extended to oligonucleotides. Some novel nucleotide analogues have been described. One of the most exciting areas in nucleic acid chemistry is the application of in-vitro selection techniques, and these have been reviewed for the first time. Biological chemistry and its needs increasingly dominate the phosphorus(v) acids’ area and the majority of novel results relate to compounds derived from phosphonic and phosphinic, rather than phosphoric acids. Numbers of studies of compounds related to inositol and to carbohydrates continue to appear, although few contain truly novel results. Phosphorus-containing analogues of amino acids V

Vi

Inlrociuction

and peptides of a wide variety of types continue to be of interest, as do phosphate isosteres, particularly those containing fluoro- or difluoro-methyl groups. Some new methods of synthesis of fluoroalkyl phosphorus compounds have been reported but more convenient methods are still urgently required. The number of reports of enantioselective and asymmetric synthesis, often but not exclusively involving P-stabilised carbanions, continues to increase. There is a growing interest in a-ketophosphonates and the number of three-membered phosphoruscontaining rings implicated as reactive intermediates continues to expand. In the hypervalent area of phosphorus chemistry a configurationally stable tris(tetrachlorobenzenedio1ato) phosphate ion has been synthesised. The growing importance of hydridophosphoranes in coordination chemistry has led to the apprearance of a useful review. The superbase properties of the commercially available proazaphosphatrane has been extended to the catalysis of the silylation of sterically hindered alcohols and phenols. The almost inexhaustible number of applications for phosphazenes ensures that interest in this area continues to be strong. Polyphosphazenes are playing an important role in the preparation of new block copolymers and in grafting processes, leading to extended applications in the production of flame retardants, membranes, hydrogels and to drug delivery polymers. The complexation of phosphazenes with a wide range of transition metals continue to be exploited. Studies of phosphazenes in organic synthesis have extended their usefulness, e.g. to the synthesis of pyridines. Their selectivity in clathrate formation with arenes is an interesting development. The multifunctionality of cyclophosphazenes continues to be exploited as starting materials for the preparation of polypodants and various dendrimers (up to 8th generation). In physical and theoretical methods there has been a notable increase in the use of recently developed techniques - most of which have trendy acronyms. Thus DRAMA 3'P NMR has been used to determine internuclear P-P distance in a phosphine sulfide 4,8-residue substituted decapeptide, and XANES has been applied to structural studies of phosphine selenides. In the mass spectral field MALDI-TOF has been found to be better than FAB for the determination of the mass spectra of nucleotide triphosphates, LA-FTICR has been used to study tris(cyanoethy1)phosphine and metaphosphates have been detected for the first time by laser photoionisation MS. ERMS was shown to be a powerful technique for the analysis of structurally similar organophosphate insecticides (OPs) and trace quantities of OPs can be determined by CI using water as the ionising agent. The 14th International Conference on Organophosphorus Chemistry (ICPCXIV), held in Cincinnati from 12 to 17 July, 1998, was highly successful and enjoyable. Cincinnati, bordered by the Ohio river, is of a manageable size and has a variety of cultural attractions, friendly people and good, cheap public transport. The enormous range of organic, inorganic and biological chemistry together with materials science covered in 240 oral presentations and 300 posters offered something of interest for everyone of the 550 participants. The biological and biologically related chemistry sessions provided the majority of the truly novel results, while the traditional organic chemistry sessions were somewhat disappointing overall. We look forward to ICPCXV in Japan in 2001.

Contents

Chapter 1

Phosphines and Phosphonium Salts By D. W. Allen

1 1

1 Phosphines I . 1 Preparation I . 1.1 From Halogenophosphines and Organometallic Reagents 1.I .2 Preparation of Phosphines from Metallated Phosphines 1. I .3 Preparation of Phosphines by Addition of P-H Unsaturated Compounds 1. I .4 Preparation of Phosphines by Reduction 1,1.5 Miscellaneous Methods of Preparing Phosphines I .2 Reactions of Phosphines I .2.1 Nucleophilic Attack at Carbon 1.2.2 Nucleophilic Attack at Halogen 1.2.3 Nucleophilic Attack at Other Atoms 1.2.4 Miscellaneous Reactions of Phosphines

18 18 19 21 23

2 Halogenophosphines 2.1 Preparation 2.2 Reactions

25 25 25

3 Phosphine Oxides and Related Chalcogenides 3.1 Preparation 3.2 Reactions 3.3 Structural and Physical Aspects 3.4 Phosphine Chalcogenides as Ligands

27 27 31 32 33

4 Phosphonium Salts 4.1 Preparation 4.2 Reactions

34 34 37

5 P,-Bonded Phosphorus Compounds

39

Organophosphorus Chemistry, Volume 29 0The Royal Society of Chemistry, 1999

vii

1

1

4 10 12

12

...

Contents

Vlll

6 Phosphirenes, Phospholes and Phosphinines

References Chapter 2

68

1 Introduction

68

2 Acyclic and Monocyclic Phosphoranes

70

3 Bicyclic and Tricyclic Phosphoranes

71

4 Hexaco-ordinate Phosphorus Compounds

79 81

Tervalent Phosphorus Acid Derivatives By 0.Dahl

83

1 Introduction

83

2 Nucleophilic Reactions 2.1 Attack on Saturated Carbon 2.2 Attack on Unsaturated Carbon

83 83 83

3 Electrophilic Reactions 3.1 Preparation 3.2 Mechanistic Studies 3.3 Use for Nucleotide, Sugar Phosphate, Phospholipid, or Phosphoprotein Synthesis 3.4 Miscellaneous

84 84 87

4 Reactions involving Two-coordinate Phosphorus

93


47

Pentaco-ordinated and Hexaco-ordinated Compounds By C. D. Hall


44

89 90

94

Quinquevalent Phosphorus Acids By B. J . Walker

97

1 Introduction

97

2 Phosphoric Acids and their Derivatives 2.1 Synthesis of Phosphoric Acids and their Derivatives 2.2 Reactions of Phosphoric Acids and their Derivatives 2.3 Selected Biological Aspects

97 97 106 110

ix

Contents

3 Phosphonic and Phosphinic Acids 3.1 Synthesis of Phosphonic and Phosphinic Acids and their Derivatives 3.1.1 Alkyl, Cycloalkyl, Aralkyl and Related Acids 3.1.2 Alkenyl, Alkynyl, Aryl, Heteroaryl and Related Acids 3.1.3 Halogenoalkyl and Related Acids 3.1.4 Hydroxyalkyl and Epoxyalkyl Acids 3.1.5 Oxoalkyl Acids 3.1.6 Aminoalkyl and Related Acids 3.1.7 Sulfur- and Selenium-containing Compounds 3.1.8 Phosphorus-Nitrogen Bonded Compounds 3.1.9 Phosphorus-containing Ring Systems 3.2 Reactions of Phosphonic and Phosphinic Acids and their Derivatives 3.3 Selected Biological Aspects 4 Structure References Chapter 5

111 111 111

114 117 120 122 123 131 133 134 136 145 147 149

Nucleotides and Nucleic Acids By Jane A . Grasby and David M. Williams

161

1 Introduction

161

2 Mononucleotides 2.1 Nucleoside Acyclic Phosphates 1.2.1 Mononucleoside Phosphate Derivatives 1.2.2 Polynucleoside Monophosphates 2.2 Nucleoside Cyclic Phosphates

161 161 161 167 173

3 Nucleoside Polyphosphates

176

4 Oligo- and Polynucleotides 4.1 DNA Synthesis 4.2 RNA Synthesis 4.3 The Synthesis of Modified Oligodeoxynucleotides and Modified Oligoribonucleotides 4.3.1 Oligonucleotides Containing Modified Phosphodiester Linkages 4.3.2 Oligonucleotides Containing Modified Sugars 4.3.3 Oligonucleotides Containing Modified Bases

184 184 188

197 20 1

5 Linkers

209

188

188

Contents

X

6 Interactions and Reactions of Nucleic Acids with Metal Ions 216 7 Nucleic Acid Structures


220

Ylides and Related Species By N . Bricklebank

231

1 Introduction

23 1

2 Methylene Phosphoraries 2.1 Preparation and Structure 2.2 Reactions of Methylene Phosphoranes 2.1.1 Aldehydes 2.2.2 Ketones 2.2.3 Ylides Coordinated to Metals 2.2.4 Miscellaneous Reactions

23 1 23 1 239 239 239 240 244

3 Synthesis and Reactions of Phosphonate Anions

246

4 Structure and Reactivity of Lithiated Phosphine Oxide Anions

249

5 Selected Applications in Synthesis 5.1 Biologically Active Compounds 5.2 Heterocyclic Synthesis 5.3 Tetrdthiafuhalene Derivatives and Related Organic Material 5.4 Miscellaneous Reactions


218

252 252 254 258 260 262

Phosphazenes By J . C. Vun de Grumpel

269

1 Introduction

269

2 Linear Phosphazenes

269

3 Cyclophosphazenes

275

4 Polyphosphazenes

28 1

5 Crystal Structures of Phosphazenes and Related Compounds 287

References

293

xi

Contents

Chapter 8

Physical Methods By R. N. Slinn and M . C.Salt

300

1 Theoretical and Molecular Modelling Studies

300 300

1.1 Studies Based on Molecular Orbital Theory 1.2 Studies Based on Molecular Mechanics and Molecular Dynamics

303 303 303

2 Nuclear Magnetic Resonance Spectroscopy 2.1 Biological and Analytical Applications 2.2 Applications including Chemical Shifts and Shielding Effects 2.2.1 Phosphorus-3 1 NMR 2.2.2 Selenium-77 NMR 2.2.3 Carbon-13 NMR 2.2.4 Hydrogen-1 NMR 2.2.5 Other Nuclei/Multinuclear/GeneralNMR 2.3 Restricted Rotation and Pseudorotation 2.4 Studies of Equilibria, Configuration and Conformation 2.5 Spin-Spin Couplings

304 304 307 308 3 10 3 10 3 10

3 Electron Paramagnetic (Spin) Resonance Spectroscopy

3 12

4 Vibrational and Rotational Spectroscopy 4.1 Vibrational Spectroscopy 4.2 Rotational Spectroscopy

3 14 3 14 316

5 Electronic Spectroscopy 5.1 Absorption Spectroscopy 5.2 Fluorescence and Chemiluminescence Spectroscopy 5.3 Photoelectron Spectroscopy

316 316 316 317

6 X-Ray Structural Studies 6.1 X-Ray Diffraction (XRD) 6.1.1 Two-coordinate Compounds 6.1.2 Three-coordinate Compounds 6.1.3 Four-coordinate Compounds 6.1.4 Five- and Six-coordinate Compounds 6.2 X-Ray Absorption Near Edge Spectroscopy (XANES)

3 17 3 17 317 318 3 19 323

7 Electrochemical Methods 7.1 Dipole Moments 7.2 Cyclic Voltammetry and Polarography 7.3 Poten tiometric Methods

325 325 325 326

31 1 31 1

325

xii

Contents

8 Thermochemistry and Thermal Methods

327

9 Mass Spectroscopy/Spectrometry

328

10 Chromatography and Related Techniques 10.1 Gas Chromatography and Gas ChromatographyMass Spectroscopy (GC-MS) 10.2 Liquid Chromatography 10.2.1 High-performance Liquid Chromatography and LC-MS 10.2.2 Thin-layer Chromatography (TLC) 10.3 Capillary Electrophoresis (CE) and Micellar Electrokinetic Chromatography (MEKC)

330

11 Kinetics

332

References Author Index

330 33 1 33 1 33 1 332

333

343

Abbreviations

BAD cDPG CE CK CPE CPmP

cv

DETPA DMAD DMF DMPC DRAMA DSC DTA ERMS ESI-MS EXAFS FAB FPmP HPLC LA-FTICR MALDI MEKC MIKE PAH QDA PMEA SATE SIMS SSAT SSIMS TAD tBDMS TFA TGA TLC TOF XANES

Benzamide adenine dinucleotide Cyclodiphospho-D-glycerate Capillary electrophoresis Creatine kinase Controlled potential electrolysis 1-(2-chlorophenyl)-4-methoxylpiperidin-2-yl Cyclic voltammetry Di(2-ethyl hexyl) thiophosp horic acid Dimethylacetylene dicarboxylate Dimethy lformamide Dimyristoylphosphatidylcholine Dipolar restoration at the magic angle Differential scanning calorimetry Differential thermal analysis Energy resolved mass spectrometry Electrospray ionization mass spectrometry Extended X-ray absorption fine structure Fast atom bombardment 1-(2-fluorophenyl)-4-methoxylpiperidin-2-yl High-performance liquid chromatography Laser ablation Fourier Transform ion cyclotron resonance Matrix assisted laser desorption ionization Micellar electrokinetic chromatography Mass analyserion kinetic energy Polycyclic aromatic hydrocarbons Hydroquinone-0, 0’-diacetic acid 9-[2-(phosphonomethoxy)ethyl] adenine S-acyl-Zthioethyl Secondary ion mass spectrometry Spermidinehpermine-N 1-acetyltransferase Static secondary ion mass spectrometry Thiazole-4-carboxamide adenine dinucleotide tert- Butyldimethylsilyl Trifluoroace t ic acid Thermogravimetric analysis Thin-layer chromatography Time of flight X-Ray absorption near edge spectroscopy

...

Xlll

1

Phosphines and Phosphonium Salts by D. W. ALLEN

1

Phosphines

1.1 Preparation I . I . I From Halogenophosphines and Organometallic Reagents. - A short review has appeared of synthetic approaches to ferrocenylphosphines possessing planarchirality, in which the reactions of lithiated ferrocenyl systems with halogenophosphines are the favoured route Among new ferrocenylphosphines prepared in this manner are the triphosphine 12, and the chiral oxazolinylferrocenylphosphines z3 and 34. The reaction of chlorodiphenylphosphine with 1,2,3-trimethylcyclopentadienyllithiumsurprisingly proceeds regiospecifically, but the outcome is very temperature dependent. Below - 10 "C, the phosphine 4 is formed, but rearranges in solution at 25 "C to give 5 via a 1,5sigmatropic transposition. Treatment of 5 with further butyllithium and then chlorodiphenylphosphine provides the diphosphine 65 as the major product, although other isomeric diphosphines can also be detected, arising from 6 by rearrangement processes5.

'.

1 R = Phor Pr'

. . Me Repph2 4

PPh2

2

5

\

3

R

6

Metallation of the bis(bromoviny1)benzene 7 with t-butyllithium, followed by treatment with phenyldichlorophosphine, provides a route to the benzoOrganophosphorus Chemistry, Volume 29 0The Royal Society of Chemistry, 1999

1

2

Organophosphorus Chemistry

phosphepin system 8, which has a tendency to eliminate phenylphosphinidene with the formation of naphthalene. Related arsenic, antimony, and bismuth systems have also been prepared in a similar way6. Two groups have reported the synthesis of chiral helical diphosphines, e.g., 9, using the organolithium route798.A new efficient route to the atropisomeric chiral diphosphines 10, some of which have the additional feature of stereogenic phosphorus atoms, has been de~eloped'.'~.Routes to new types of chiral atropisomeric diphosphenes, e.g., 11 and 12, have also been reported''. Treatment of the diaza-

7

@

Ar'-P P-Ar' A; A '? 10 R = M e o r O M e Ar' = Ph or ptolyl A$ = alkyl, 2-fury1 or 2-thienyl

8

9

M e q - P P h 2 '

N

Me73-p \ /

11

12

phospholidine 13 with t-butyllithium, followed by phenyldichlorophosphine, results in an unusual rearrangement with the formation of the chiral diphosphine 14, a new class of C2-symmetric ligand 12. The reactions of o-lithiophenoxides with chlorodiphenylphosphine,followed by treatment with chlorotrimethylsilane, give the silylated phosphinophenols 15 from which the silyl group is easily removed by treatment with methanol to give the free pho~phinophenol'~. The same strategy has been used for the synthesis of the phosphinonaphthols 1614.In related work, it has been shown that o-sodiophenyldiorganophosphiniteesters rearrange to form the sodiophosphinophenoxidesl?'. Ortho-lithiation of an O-protected rn-fluorophenol, followed by treatment with phosphorus tribromide and aqueous acid deprotection, has given the phosphinophenol 18. In the presence of potassium t-butoxide in an aprotic solvent, this is converted into the non-planar system 19, which exhibits pyroelectric properties 16. An organolithium route to the alkynylphosphine 20 has been developed. The same paper also reports a new route to the lithiated alkynylphosphine 21 and a study of its reactivity towards ele~trophiles'~. Diastereoselective lithiation of

I: Phosphines and Phosphonium Salts

3

13

14

15 R' = Me, Et, But, Ph or N M e R2 = H, Me or But R3 = H or But

16 R' = H or NMe2

17 R = Me, Et, Ph or Pr'

R2 = Ph, But, Pr' or NMe2

chiral hydrazones provides a novel enantioselective synthesis of chiral phosphines, e.g., 22, which may then be transformed into chiral 2-phosphino-ketones and h alcohol^'^*'^. Organolithium reagents have also been utilised in the synthesis of the chiral phosphines 23*', the heteroarylphosphine 2421, and further

18

19

20

21

PR22 22

23 n = O o r l

synthesis of phosphinocarborane derivatives22.Selective P-C coupling occurs in the reaction of the lithium phosphinoenolate 25 with chlorodiphenylphosphine, to give the new diphosphine 2623. Full details of the synthesis of bis- and tetrakis-(diphenylphosphino) tetrathiafulvalenes e.g., 27, have now appeared24. Both Grignard and organolithium procedures have been employed in the synthesis of a wide range of functionalised arylphosphines, e.g., 28, which can be linked to a chiral skeleton25, and also in the synthesis of the chiral aminoakylphosphines 2926927.A much improved route to the rn-aminoarylphosphine 30 is provided by the reaction of N-bis(trimethylsily1)-protected-aminophenyl

4


ph2pk fiNPh2

Li[PhpPCH-C=NPh~] :I 0 25

R

Ph2P

0 26

27

R

-YNMe2 R

R

28 R = Br, -C=CSiPhs, -C=CPh or Ph

'

'w

29 R = Pr'or Ph

30

n = 1-3

Grignard reagents with halogenophosphines, followed by desilylation with methanol. Some of these compounds have also been prepared directly from miodoaniline by treatment with either phenylphosphine or diphenylphosphine in the presence of a palladium complex. The amino group has subsequently been converted into a guanidinium cationic moiety, rendering the phosphine watersoluble2*. Grignard procedures have also been used in the synthesis of the chiral secondary phosphine 3129, and of (E)-diphenyl(l-phenyl-2-bromovinyl) phosphine3*. A Grignard-like procedure has been used in the synthesis of silylphosphines e.g., 32, via the reactions of hindered halogenosilanes with magnesium and the appropriate halogenophosphine. The same strategy has also been applied in the synthesis of related germyl- and stannyl-phosphines3' . Me Me Me 31

Me 32

Triphenylstannyldiphenylphosphine has been prepared via the use of sodium triphenyl~tannide~~. Full details have now appeared of the use of organozinc reagents bearing reactive functional groups in the synthesis of polyfunctional and chiral p h o ~ p h i n e s ~Applications ~. of organotitanium and organozirconium reagents have also appeared. Thus, treatment of the titanacyclobutenes 33 with two equivalents of dichlorophenylphosphine has given the diphosphacyclopentenes 3434. In contrast, reactions of zirconacyclopentanes with chlorodiphenylphosphine, even when present in quantities sufficient for reaction with two zirconium-carbon bonds, afford only a monophosphine, e.g., 3535. I . 1.2 Preparation of Phosphines from Metallated Phosphines. - The first soluble crystalline potassium salt (36)of a primary phosphine has been prepared, and its

I : Phosphines and Phosphonium Salts

5 Me

33 R = Ph, Me or Et

34 R = Ph, Me or Et

35

structure studied by X-ray ~rystallography~~. A series of Iithiopolyphosphides, e.g., 37, has been prepared and structurally ~haracterised~’. Lithium bis(triphenylsily1)phosphide has been shown to exist as a dimer in the solid state. The related bis(tri-isopropylsily1)phosphide exists as a cyclic t ~ i m e r ~The ~. reaction of bis(chloromethyldimethylsilyl)amine with three equivalents of lithium diisopropylphosphide gives the phosphinoamide salt 38 under certain conditions and its solid state structure has been studied39.

L~[(P~$P)~P]

36

37

[LiN(SiMe2CH2PPr$)2 12LiCl

38

Interest has continued in the generation of phosphide anions from elemental phosphorus and phosphine, under superbasic condition^^-^^, and also in the application of borane-protected phosphide reagents in synthesis. These reagents are easily generated, e.g., by alkali metal cleavage of phenyl group from the triphenylphosphine-boranecomplex, and can subsequently be applied in reactions with alkyl halides and tosylates to form new phosphines, from which the protecting group is easily removed. Thus, in the past year, they have been used in the synthesis of alkyldiphenylphosphine-boranecomplexes43,various dialkylaminophosphines, e.g., 39, (capable of further elaboration)44, and a range of chiral diphosphines, e.g., 4045,4146,4247748,4349, and 44, isolated as the dioxide5’. The reaction of the borane complex of lithium dicyclohexylphosphide with o-chloroalkyltrialkylammonium salts provides a route to a new family of water-soluble phosphines, e.g., 45, of interest in homogeneous catalysis5’. Well established reactions of phosphide reagents, notably lithium diphenylphosphide, with alkyl halides and sulfonate esters, have again featured as the key P-C bond-forming step in the synthesis of new phosphines, many of them chiral, including 46 (in which four stereogenic carbons dictate the orientation of the P-phenyl groups)52, the camphor-based systems 4753,the carbohydrate-based systems 4854,4955,and 5056, the triphosphines S157 and 5258, and the phosphinoalkylnitriles 5359.The synthesis of the phosphinoaldehyde 54 has been re-investigated, and an improved route developed, which involved the reaction of lithium diphenylphosphide (rather than sodium diphenylphosphide) with bromoacetaldehydediethylacetal as


6

42 X = 2,6-pyridinediyl, 1,&naphthalenediyl or 2,2'-biphenylylene

43

44

45

P h 2 P q . * o M e

PPh2

ti

46

49

N LPPh2 52

'OH

OH 48

47 R', R2, R3 = H or PPh2

50

R2P(CH2)"CN

PhZPCHzCHO

53 R = Ph, Pr' or Cy n = 3,6or 10

54

the key step6'. The reaction of lithium diphenylphosphide with arenesulfonyl chlorides results in the formation of the diphenylarylsulfophosphamides 55, which have been shown to undergo cathodic cleavage of the phosphorus-sulfur bond, to give, eventually, diphenylphosphinic acid and the arenethiol, characterised as the thiomethyl ether61. The lithium phosphaguanidine system 56 has been isolated from the reaction of lithium bis(trimethylsily1)phosphide with diphenylcarbodiimide62. With boron trihalides, lithium bis(trimethylsily1)phosphide gives the dimeric systems 5763.An improved route to tris(trimethylsily1)phosphine involves the reaction of dichloro(piperidino)phosphine, trimethylchlorosilane, and lithium powder in refluxing THFa. Dimetallophosphide

7

I : Phosphines and Phosphonium Salts ?h Me3SiN

,Ph

FNt

0 II Ar-S-PPh2 II 0

MesSi,

y.:'i+ Me3SiN Ph

55

X ,B\

,SiMe3

~ e 3 S i /'\B/P'SiMe3 X 57 X = C I o r B r

Ph 56

reagents, e.g., dilithium phenylphosphide, have received wide application for the synthesis of heterocyclic phosphines, e.g., the 7-phosphabicyclo[2.2. llheptanes 5865,66,the chiral phosphetane 5967, the chiral bicyclic system 6068,and the bis(phospho1ane) 6169.These reagents have also been utilised in the synthesis of chiral, acyclic polydentate phosphine ligands, e.g , 6270. Monometallation of organosilylphosphines, followed by treatment with alkyl or alkenyl halides, has

59

58 R = M e o r P r '

60

Q

d

Me0

,

CH2CHCH2PPh2

PhP, Q h 3 v l e 1

OMe Me0 61

/

CH2CHCH2PPhz I

Me 62

given a range of reactive silylphosphines, some of which have been transformed into heterocyclic phosphines in subsequent reactions71. A new stereoselective synthesis of phosphiranes 63 is provided by the reaction of monolithiated primary phosphines with ethaneditosylates, followed by metallation of the intermediate secondary phosphine with butyllithium7*. Monolithium phenylphosphide is the key reagent in the synthesis of the bis(sec0ndary)phosphine 64, which, on treatment with four equivalents of butyllithium, gives rise to the macrocyclic system 6573. Interest in the chemistry of phosphines metallated at carbon has also been

63 R = Ph, mesityl or 1-adamantyl

64

65

8


maintained. The Ph2PCH2Li. TMEDA adduct has been shown to exist as a dimer in the solid state, rather than a monomer, as previously reported74. The reactions of lithiomethyldimethylphosphine with halogeno-phosphines, -arsines, -stibines, and bismuthines enable the synthesis of a wide range of polydentate donor l i g a n d ~ ~Karsch's ~. group has also explored the reactions of lithium bis(phosphin0)methanides with organo-silicon, -germanium, and -tin halide^^^-^^. Treatment of spiro[2.4]hepta-4,6-dienewith phenylphosphine and butyllithium results in the formation of metallated phosphine 66, which with ferrous chloride, gives the ferrocenophane 6779.The ferrocenophane 68 has been shown to undergo a living anionic ring-opening polymerisation on treatment with butyllithium, to form the phosphinoferrocene polymer 6980.The phosphinoamidomethanide 70 has been prepared from the reaction of lithium bis(trimethylsily1)phosphide with benzonitrile. Its reaction with trimethylsilyl chloride provides a novel access to the phospha-alkene 718'. The borane-protected phosphinomethanide 72 has been used in the synthesis of the chiral tridentate ligand 73, via its reactions with 2,6bis(bromoethyl)pyridine82.

66

Q Fe

P-Ph

0 -I-/

67 Ph1

BuLi

I

Fe

THF

68

69

Me3SiP=C

Ph

N(SiMe&

[PhC(PSiMe3)( NSiMe3)lLi

71

70

(3L3 CH2Li

72

OMe

73

Me0

While lithiophosphide reagents dominate this area of phosphine synthesis, applications of sodio- and potassio-phosphide reagents continue to appear. The

9

1: Phospliines and Phosphonium Salts

photo-assisted SRN1 reactions of sodium diphenylphosphide with halogenoadamantanes have been studieds3, and a sodium diphenylphosphide-tosylate route has been used in the synthesis of the chiral diphosphine 7484. Conventional applications of potassium diphenylphosphide have been made in the synthesis of the diphosphines 7585,the chiral 3-diphenylphosphinopyrrolidine7686,the chiral ~~, phosphine 77 (obtained in an improved four-step route from D - m a n n i t ~ l ) the phosphinoalkylarenes 7888,and also in the phosphino-functionalisation of silsesquioxanesp9. Chiral, water-soluble, secondary phosphines, e.g., 79,capable of further elaboration to chiral tertiary phosphines and diphosphines, have been obtained from the reactions of primary arylphosphines with fluorobenzenesulfonates, displacement of the fluorine substituent occurringg0. In related work, displacement of fluorine from fluorophenylacetic acids or fluorobenzylamines with potassium diorganophosphide reagents has given the functionalised chiral phosphines 80, which have then been transformed into related phosphino-functional amino-acid systems". An anionic complex of potassium diphenylphosphide with boratabenzene has been characterised, and its coordination chemistry studied92. Metallophosphide reagents have also found extensive use in the synthesis of

t

0

PPh2

R ;

;

2 h p Ph2P

74

78 X = O o r C H * Y=HorF

75 R = H, OMe or OEt

79 Ar = Ph, mesityl or Pt3C8H2

H

76

xo>+pph H

0

n

80 X = NH2 or C02H

systems in which phosphorus is bonded to atoms other than carbon, e.g., boron, silicon, germanium, and tin. Many of these have novel cage-like structures, often involving several different p-block elements. Examples of phosphorus-silicon system^^"^^ include 8193and 8294.The reaction of a diphosphide reagent with tin tetrachloride resulted in various products, including the cage-compound 8399. Other phosphorus-tin heterocyclic systems have also been describedlm. Both linear'" and cyclic'o2 phosphinoborane systems have been characterised, and a range of cage systems involving both phosphorus and boron, together with either silicon, germanium, or tin, has also been d e s ~ r i b e d ' ~ " ' ~ ~ .


10 Ph

R

P $ S i M e p\ 81

Ph

R

P-R /,p-pJ ClSn R R SnCl S-i Me2

Me2 82

\P-R R

I

R

83 R = Bu'

The synthesis and characterisation of organophosphide derivatives of other metallic elements continues to attract attention, and the past year has seen further examples of systems involving aluminium'06-'08,gallium'09-'", indium' I 13, titanium' 14, and zirconium' 15-' 17. In addition, organophosphide derivatives have also been described. of niobium' 18, tantalum' 19, and

'

'

1.1.3 Preparation of Phosphines by Addition of P-H to Unsaturated Compounds.Mechanistic aspects of the addition of P-H bonds to alkenes and alkynes have been reconsidered in the light of new activation methods. In the case of additions of diphenylphosphine, radical and ionic routes are indistinguishable, a duality of mechanism being apparent, the coexistence of the two routes bringing about a competition which depends on conditions'22. The additions of phosphine to simple alkenes, and bicyclic secondary phosphines, e.g., 9phosphabicyclo[4.2. llnonane, with linear, long chain, terminal alkenes, has been , ' * ~phosphines . 84 and 85 have studied by an in-situ 3 1 PNMR t e c h n i q ~ e ' ~ ~ The been isolated from the free radical addition of phosphine to ~t-pinene'~'.The key step in the synthesis of the chiral triphosphine 86 is the addition of diphenylphosphine to the bis(-)-menthy1 ester of a benzylidene malonic acid'26. Photochemical addition of diphenylphosphine to N-ally1 groups is the crucial step in the synthesis of the triphosphine 87127.Photochemical initiation has also M G P H ~

M &

CH2PPh2 Ph-CH-Cv I PPh2 CH2PPh2

84

85

86

87

been used in the addition of diphenylphosphine to trichlorovinylsilane, giving the phosphine 88, a key intermediate in the synthesis of phosphinoalkylfunctionalised silsesquioxanes' 28. Primary and secondary phosphines bearing

11

1: Phosphines and Phosphonium Salts

trimethylsilyl groups appear to behave normally in addition reactions with alkenes. This approach has been used in the synthesis of heterocyclic systems, e.g., 89'29,and new cycloalkylphosphines, e.g., 90130. Addition of primary and secondary phosphines to alkenes bearing water-solubilising groups has given a new series of water-soluble phosphines and diphosphines, e.g., 9113', 92132,and 93133.Another route to water-soluble systems is offered by the base-promoted addition of bis(primary)phosphines to vinylphosphonates, to give 94'34. In related work, reduction of bisphosphonates with lithium aluminum hydride to generate new primary phosphine functionalities, followed by their reaction with formaldehyde has provided further water-soluble systems, e.g., 95l 35. The reaction of diphenylphosphine with aromatic o-hydroxyaldehydes and a diester of a diboronic acid has given 1,3,2-dioxaborinane systems, e.g., 96 which bear R

R - P E X

0 Ph2P

Me

Na03S\

NH-A-CH2S03I Me 91 M+= Na+or R4N+

M+

<S03Na P

%SO&

N a O 3 S Y p 92

Ho+r\/F k % P p

HO

p

93 n = 1 o r 2

P

b

(H O C H 2 ) 2 P r \ S / X ~ n P ( C H 2 0 H ~ 2

95 X = (CH2)3 or &eH4

d

90 R = Me3Si or H

89 R = H or Me3Si X = PPh, PNEt2 or SiMe2

88

2

nOH

12


phosphino fun~tionalities'~~. Interest in P-H addition to coordinated alkenes has continued, with examples of regiospecific addition to coordinated allenyl systems'37, and addition of secondary phosphines to cationic dienyl tricarbonyl iron complexes'38, having appeared. A study of platinum catalysis in the addition of a hindered primary phosphine to acrylonitrile has provided further insight into the m e ~ h a n i s m ' ~ Addition ~. of diphenylphosphine to a P-coordinated propargylphosphine has also been described". Borane adducts of primary and secondary phosphines also behave normally in hydrophosphination of alkenes. Thus, e.g., both !I7 and 98 have been isolated from addition of a boraneprotected primary phosphine to methyl acrylate and dimethyl vinylph~sphonate'~'. Similarly, the borane adduct of diphenylphosphine adds to a diene obtained from D-mannitol to give the chiral diphosphine !Ell4*.

+

R - P P X BH3 97 X = C02Me or P(O)(OMe)2 R = Me or Ph

98 X = C02Me or P(0)(OMe)2 R = Me or Ph

99

I . 1.4 Preparation of Phosphines by Reduction. -- Although relatively few examples have appeared this year, trichlorosilane has remained the reagent of choice for reduction of phosphine oxides, usually in the final stage of a synthetic route. Examples of phosphines prepared in this way include the new chiral phosphetanes and the atropisomeric diphosphine 102145.A new route to 'chiraphos' (103) involves as the key step the reduction of the diphosphine oxide 104 with sodium borohydride, to give 'chiraphos dioxide', which after resolution, is then reduced to 'chiraphos' using trichl~rosilane'~~. A range of secondary phosphines bearing bulky groups has been obtained by reduction of related monochlorophosphines with lithium aluminum h ~ d r i d e ' ~Treatment ~. of the alkenylphosphine 105 with ethylmagnesium bromide in the presence of bis(tripheny1phosphine) nickel(I1) chloride gave (E)-diphenyl(4undecenyl)phosphine, cleavage of the methoxy group having taken place. The alkylmagnesium halide was shown to be the exclusive hydride source. In contrast, treatment of 105 with either methylmagnesium or phenylmagnesium chloride gave a mixture of 106 and 107'48. 1.1.5 Miscellaneous Methods of Preparing Phosphines. - The synthesis and properties of phosphorus-containing cryptand ligands has been reviewed'49. The basic principles for the synthesis of functionalised phosphorus-containing heterocyclic systems have been summarised, relating to the chemistry of phosphabicyclohexanes, dihydrophosphinines, phosphabicyclooctadienes, and phosphabicyclooctenes'50. Ethylene acetals (108) of the 9-oxa-2phosphabicyclo[4.4.0]-5-one system have been preparedI5'. Methods for the

13

I : Phosphines unti Phosphonium Salts

Q+

PPh2

OYPPh

101 n = O o r l

100 X = O o r S

102

0 Met;; PhpP

OMe

Ph2P

II

0

H

103

R

R

M e %

Ph

105

104

I

/ 106 R = M e o r P h

p/ Ph I Ph

Me

p/ Ph 107 R = M e o r P h

I Ph

synthesis of P-chiral monophosphines bearing a bulky group have been appraised, and a range of compounds bearing the 2-adamantyl group prepared, An easy route to starting from P-chlorooxazaphospholidine52. tris(trifluoromethy1)phosphine has been developed, involving a three component system consisting of tris(diethylamino)phosphine, bromotrifluoromethane and triphenylphosphite, in HMPA'53. A very similar approach has been used in the synthesis of the unsymmetrical diphosphine 109'54. Addition of hydrophilic thiois to vinylphosphines has been employed in the synthesis of water-soluble phosphinoethyl sulfonatoalkyl t h i o e t h e r ~ ' ~ ~Substitution, . addition, and rearrangement reactions of easily accessible derivatives of carbohydrates with diphenylvinylphosphine and 2-mercaptoethyldiphenylphosphine have given a series of chiral bidentate P-thioethylphosphine ligands, e.g., 110'56. Glycosidation of 2-hydroxyphenyldiphenylphosphineaffords a simple route to carbohydratesubstituted phosphines, e.g., 11 1 '". Other routes to carbohydrate-phosphine systems have also been de~cribed'~'.A brief review has appeared of the synthesis, chemistry and application in catalysis of atropisomeric phosphines, in particular dinaphthophospholes and dinaphthophosphepins' 59. Further atropisomeric systems have been prepared by phosphitylation of the phenolic group of the phosphine 112160*'61. Routes to the chiral ferrocenyldiphosphines 113 have been developed, via the use of the chiral oxazaphospholidine borane 11416*.Routes to other chiral ferrocenylphosphines have also been developed, including the boranato-functionalised systems 115163, and the Cz-symmetric diphosphine 116,having only the planar chirality of the ferrocene system'@. Full details have now appeared of the palladium-promoted asymmetric Diels-Alder reaction between 1-phenyl-3,4-di-

'


14

108

109

111 R'=HorOH, R2=HorOH, R3=OHorNHAc

112

methylphosphole and substituted vinyldiphenylphosphines, which give the Pchiral diphosphine (117, E = P)16'. Related work involving cycloaddition to vinyldiphenylarsine has given the chiral phosphinoarsine system (1 17, E = As; R' = R2 = H)166. Similar addition of phenyldivinylphosphines have given the diphosphines 118, which have two phosphorus and three or four carbon stereogenic Quaternization of bis(dipheny1phosphino)ethane with o-

116

117 R', R2 = H or Me

118 R'

=

H or Me, R2 = H or Me

iodopropyltriarylphosphonium salts to give the diphosphonium salts 119, followed by alkaline hydrolysis, and final reduction of phosphine oxide moieties with trichlorosilane, are the key steps in the synthesis of a range of unsymmetrical triphosphine ligands (120)169. The presence of o-methoxyphenyl substituents in the diarylphosphinite-borane adducts 121 results in a remarkable rate enhancement effect in their reactions with organolithium reagents to form the chiral phosphine-boranes 122I7O.Double-labelling techniques have established an intra-

15

1: Phospiiines and Pliosphonium Sults

BH3

BH3

t

t

A I ~ ~ ( C H ~ ) ~ ~ ( C H ~ ) ~ AP~P~~P~( C H Z ) ~ P ( C H ~ ) ~ PPh-P-OC6HII P~~ I I Ph2 21Ph Ar 119 120 Ar = Ph, pCIC6H4 or PFCsH4 121

Ph-P-I7 I Ar 122

molecular mechanism which involves pentacovalent P intermediates for the rearrangement of the o-lithiophenylalkyl esters 123 to the phosphines 124 and related derivative^'^'. The chemistry of phosphinobenzaldehydes, notably 125, has continued to develop. Further examples of Schiff's base condensations to give hybrid ligands have been described, e.g., 12617*,127173, and 128'74.The phosphine 125 has been converted into the cyclam system 129 bearing a pendant

124

123 Ar = Ph or B-naphthyl n = 1 or2 X = lone pair or 0 or BH3

125

Me

Ph2P

PPh2 126

CH=NCH2CHz 127

128

129

p h o ~ p h i n e ' ~Schiff's ~. base formation is also the key step in the synthesis of new hybrid, chiral ligands from the phosphines 130176and 131177. Conformational diastereoisomerism in the phosphino-imines 132 has been studied by NMR 178. Silylation of the diphosphinodiol 133 (obtained by de-acetalisation of the chiral diphosphine DIOP) has given a range of new chiral ligands 134, in which the bulky silyloxy groups fix the chiral en~ironment'~'.The reaction of hydroxyalkyldiphosphines with o-sulfobenzoic anhydride in the presence of a base provides a new route to chiral sulfonated, water-soluble, phosphines, e.g., 135180. The heteroarylphosphine 136 has been obtained via the direct reaction of an Nprotected aminothiazole with phosphorus tribromide'*'.

16

Organophosphorus Chemistry OMe H HO"P (' Ph2 HO& 130

131

R 3 S i O e PPh2

R3Si0

132

'

PPh2

133

0

2 h pf & !

H 134 R3Si= Me3Si, ButMe2Si, Pr'3Si or Ph3Si

PPh2

H

S03-M+

H

PPh2

2

N

4

136

135

A standard combinatorial synthetic approach has been used to give a 63member library of phosphine-functionalisedpeptides. The approach is based on the peptide chemistry of phosphino-aminoacids, e.g., 137, the phosphorus of which is protected (as the sulfide) during the synthetic procedure, and then deprotected via the use of iodomethane, followed HMPT182.Further examples of polymer-based phosphines have been d e ~ c r i b e d ' ~ ~The * ' ~synthesis ~. of phosphino-terminated dendrimers continues to attract attention, and several new systems have been ~ r e p a r e d ' ~ ~A-useful ' ~ ~ . approach is the surface functionalisation of dendrimers bearing secondary amino groups, using hydroxymethyldiphenylphosphine, to form aminomethylphosphine ~ n i t s ' ~ ~ ~ ~ . approach A "similar has been used in the phosphino-functionalisation of aminoalkyl-P-cyclodextrin systems'88. Treatment of ferrocenylmethyltrimethyIammonium iodide with tris(hydroxymethy1) phosphine has given the ferrocenylmethylphosphine 138 as an air-stable solid, which undergoes the usual transformation reactions of hydroxymethylphosphines, enabling the synthesis of a number of new systems, e.g., 139189. On treatment with aqueous sodium metabisulfite, 138 is converted into the primary phosphine 140, an air-stable orange solid"*. Formylation of the triphosphine 141 has given the new, water-soluble triphosphine 142'". Stannylation of hydroxyalkylphosphines has also been reported, to give, e.g., 14319*. @-CH2P(CH20H)2

0

I

I

P

Fe

@

137

Ph-P

PH2 L P H 2 141

138

@ PP(CH20H)z

Ph-pLP(CH20H)2 142

139

@

R Me2P- CH OSnMe3 143

140

17


Intramolecular coupling of bisalkynylphosphines occurs in the presence of a transient zirconocene-benzyne complex to give the zirconocycle 144, which, on subsequent treatment with hydrogen chloride or phenylantimony dichloride, gives The the phosphete 145 and the benzostibinine phosphete 146, re~pectively'~~. utility of phosphazirconacycles, e.g., 147, in metallacycle transfer reactions leading to main group phosphacycles, has been explored. Thus, e.g., with phenyldichloroA P16-macrocyclicsystem phosphine, 147 yields the cyclotetraphosphine 149, has been obtained from the reaction of o-bis(phosphin0)benzene with a trihydridozirconium complex'95. The MO(CO)~ fragment has been used to protect tripodal phosphines, e.g., 150 from oxidation and P-C cleavage during functionalization of their cyclohexane backbone. The C-functionalised phosphines are liberated from the complexes by a combined photochemical-oxidation process196. Ph

Ph

cP2

I

Ph

144

Ph

A

Ph 146

145

Ph 147

Ph 1

R

P Ph- -.P< )P--Ph

R

P h z P w P P h 2

P

A

Ph 148

4

PhpP' 150 R = CH20H, CH20Me or CH20CH2CH20Me

Full details have now appeared of the stereoselective synthesis of 1,5,9triphosphacyclododecane systems by oxidative liberation from molybdenum and chromium complexes of the macrocycle, obtained by coordination-template controlled reactions197. Molybdenum complexes have also been used in the coordination-template dependent synthesis of the macrocyclic P,S system 15119*. A non-template synthesis of the 14-membered P2S2 macrocycle, 152, isolated in two isomeric forms, has been describedlW. Halogenation of the cyclometallated phosphine 153 leads to a rearrangement, with the formation of the diphosphinobiphenyl system 154, from which the free diphosphine can be liberated

Q

Ph

cp3

PR2AuX

S

WS 151

3

Ph 152

153 R = PhorEt

opR 154

18


on treatment with cyanide2''. An electrochemical route to diphenyl(tributy1stanny1)phosphine has been developed, which involves the electrolysis of a mixture of chlorodiphenylphosphine and tributylstannyl chloride at a sacrificial magnesium anode in DMF201. White phosphorus undergoes alkylation and arylation with organic halides in the presence of electrochemically-generated Ni(0) complexes, to give mixtures of phosphines and the related phosphine oxides202.Arylation of primary or secondary phosphines has been achieved on treatment with aryl iodides (bearing a wide variety of substituents) in the presence of a Pd(0) complex, enabling the synthesis of functionalised arylphosphines, e.g., W 2 0 3 . The phosphine 156 has been prepared via the reaction of lithiomethyl(pheny1)sulfide with triphenylphosphite, and then converted into chalcogenide derivatives2M, and also complexed with gold205. Phosphonato-functionalised triarylphosphines, e.g., 157, have been obtained by the reaction of lithiophenylphosphines with diethyl phosphorochloridate. Hydrolysis of the phosphonate ester provides water-soluble phosphines, e.g., 158206.A route to the chiral phosphinoalkyloxazolines 159 has been developed which involves the reaction of a P-phosphinopropionic acid derivative with an amino-acid followed by cyclisation of the intermediate amide-acid207.A range of bulky phosphines, e.g., 160 has been prepared, which possess functionalities which make possible their attachment to a chiral system, creating a chiral 'pocket' which act as mimics of natural ion-channel systems208.Routes to the new C2-symmetrical diphosphines 161 and 162 have also been developed209. 1.2 Reactions of Phosphines 1.2.1 Nucleophilic Attack at Carbon. - The generation of reactive intermediates

by the addition of phosphines to unsaturated esters, and their subsequent reactions, continues to attract interest. Adducts of phosphines with buta-2,3dienoates and but-2-ynoates are key intermediates in the formation of [3 + 21 cycloadducts of the unsaturated esters with [ 6 O ] - f ~ l l e r e n e ~ In ~ ~similar ~ ~ " . vein, the reaction of triphenylphosphine, dimethyl acetylenedicarboxylate, and [60]fullerene has given a methano [60]-fullerene system in which a stable ylide moiety is attached to the c60 unit212. The formation of vinylphosphonium salts by protonation of the initial adduct from the reaction of triphenylphosphine with dimethyl acetylenedicarboxylate is the key step in directing the course of reactions of the above system with butane-2,3-dione monoxime, and 3chloropentanedione, Triphenylphosphine also catalyses the reactions of methyl 2,3-butadienoate with aromatic or heteraromatic Ntosylimines, giving nitrogen heterocycles. The initial key intermediate is the zwitterion 163215.The conjugate addition of oximes to ethyl propiolate to give 0vinyl oximes is catalysed by triphenylphosphine, this reaction presumably also involving a vinylphosphonium intermediate2I6. Transition state structures for the addition of maleic anhydride and methyl phenylpropiolate to 1-phenyl-3,4dimethylphosphole have been investigated by a computational study2". Full details have now appeared of the characterisation of the zwitterionic adducts 164 from reactions of tri-isopropylphosphine with 2-cyanoacrylates, and of their subsequent reactions with a variety of reagents218. The molecular structures of

I: Phosphines und Phosphonium Sults

PhpP q C o ” 155

19

(PhSCH2)3P

C02H

156

157

159 R’ = H or Ph, R2 = Me, PhCH2, Pr‘ or Ph

158

160

162 X = CH2 or NMe

161

zwitterionic adducts of acrylic acid with triphenylphosphine and 1,2bis(diphenylphosphino)ethane, respectively, have been studied by X-ray techniques2I9. The phosphine-catalysed dimerisation of alkyl acrylates has been reviewed220.The reactions of phosphines (and other trivalent phosphorus species) with quinones continue to attract interest, and this area has also been reviewed22’. The stabilised ylide 165 has been isolated from the reaction of triphenylphosphine with 2,6-di-t-butyl- I ,4-benzoquinone. In contrast, the related reactions of triphenylarsine and triphenylstibine take a different course, aryloxyarsonium betaines 166, and the stibonium ylide 167, resulting222. 1.2.2 Nucleophilic Attack at Halogen. Nucleophilic attack at iodine is probably initially involved in the reaction of the iodoketone 168 with triphenylphosphine, which, at 80°, results in the formation of the alkoxyphosphonium salt 169. On heating to 150°, this eliminates triphenylphosphine oxide with the formation of the cycloalkyl iodide 170223.Cyanogen iodide acts as a positive iodine source in its reaction with triphenylphosphine. providing a reagent system which transforms alcohols into iodoalkanes in high yield224. A mild and efficient method for ~

20


164 R = M e o r E t

163

0-

165

166

168

167

169

170

converting alcohols and tetrahydropyranyl ethers into bromides with inversion of configuration is provided by a combination of triphenylphosphine with 2,4,4,6tetrabromo-2,5-cyclohexadienonein dichloromethane or acetonitrile, which is reported to involve the phosphonium salt 171 as the key intermediate225.The structures of tertiary phosphine-iodine adducts have been reconsidered in the light of detailed spectroscopic and conductivity studies. The adducts are now described in terms of a charge-transfer complex of a donor iodide ion with the acceptor iodotriorganophosphonium cation, rather than a discrete ionic structure or a molecular charge-transfer complex. Previously reported solution data for the triphenylphosphine-iodine system, for which the ionic formulation was favoured, are now said to be in agreement with the formation of products of hydrolysis of the adduct in the presence of traces of water226.A structural study of the iodine adduct of butyl(isopropy1)iodophosphine has revealed a largely ionic structure involving bridging polyiodide anions227.A similar solid state study of the adduct of chlorine and triphenylphosphine formed in dichloromethane solution has revealed a novel dinuclear ionic structure 172, involving long chlorine-chlorine contacts228.

Ph$Br

O*Br

Br 171

[PhsbCI-

-el- -CIbPh,]CT 172

21

I : Phosphines and Phosphonium Subs

1.2.3 Nucleopltilic Attack at Other Atoms. - A convenient route to phosphineborane complexes is afforded by treatment of N-methylmorpholine-borane derivatives with the p h o ~ p h i n e ~ ~The ~ . crystal structure of the dicyclohexylphosphine-boranecomplex has been reported230. Stable, distillable borane adducts of primary phosphines have been obtained by an exchange reaction with the borane adduct of dimethyl sulfide, and their reactions with aldehydes explored23'. The hydroboration of o-alkenyldiphenylphosphines has been investigated. In the presence of an equimolar quantity of borane, the expected phosphine-borane complex is formed. Attack on the double bond only occurs in the presence of excess borane. With the bulky borane, 9borabicyclononane, cyclisation products, e.g., 173, are formed as a result of an intramolecular addition to the double Reversible adduct formation between phosphine and primary phosphines with triarylboron compounds has been reported, the adduct decomposing on heating234.A range of adducts of 1,1'-bis(dipheny1phosphino) ferrocene with boranes, thiaboranes, and carboranes has been described235.Adducts of tris(trimethylsi1yl)phosphine with gallium halides236 and phenylaluminuim compounds have been ~haracterised~~~.

173

n = l or2

Two studies have been reported on mechanistic aspects of the attack of phosphines on the oxygen-oxygen bond of ring-substituted 1, 2-dioxolanes. Factors which control regioselectivity of attack have been explored238,and rate studies are consistent with the initial formation of metastable phosphoranes as the rate-determining step, these then undergoing decomposition by several ionic routes239.The reactions of phosphines with dibenzoyl peroxide have been studied by ESR techniques and phosphorus-centered radical intermediates trapped240. The oxidation of triphenylphosphine by hydrogen peroxide in pyridine has been shown to be catalysed by ir0n(II1)~~'. A study of the oxidation of triphenylphosphine with potassium peroxodiphosphate in the presence of '*O-labelled water has shown that the phosphate salt is the origin of the oxygen of the P=O bond242. A pyrazine-based polymeric complex of oxodiperoxochromium(V1) is a new stable, mild, efficient oxidant and has been shown to oxidise phosphines to the related phosphine Triarylphosphines are thought to attack at carbonyl oxygen of the chromene-dione system 174, and the reactions lead eventually to the quite surprising formation of methyl diarylphosphinate esters, and the arylamine 175. Trialkylphosphines behave differently, the phosphinamide 176 being formed244.Phosphine-cleavage of sulfur-sulfur bonds has been utilised for the synthesis of stable thiobenzaldehyde~~~', and for the initiation of ringopening polymerisation reactions246.

Orgmophosphorus Chemistry

22

174

175

176

Mitsunobu chemistry continues to attract attention, and many new synthetic applications have appeared. Its applications in alkaloid synthesis have been reviewed247.The formation of benzoic anhydride in Mitsunobu-promoted esterifications involving benzoic acid is a troublesome side reaction, but anhydride formation can be prevented by the use of p-nitrobenzoic acid as an alternative248. The effect of the microenvironment surrounding the active sites on kinetics and yield in polymer-supported Mitsunobu esterification systems has been exp l ~ r e d Combinations ~~~. of triphenylphosphine with diethyl azodicarboxylate and tributylphosphine with azodicarbonyldipiperidide have been used to promote an unusual tandem cyclisation - Stevens rearrangement process250.An unusual intramolecular Mitsunobu procedure has been described in which an amide acts as the n ~ c l e o p h i l e ~ ~Improvements ’. on the original conditions have been introduced for sulfonation of alcohols with inversion of configuration by the Mitsunobu reaction252. A double inversion Mitsunobu process, involving sulfonation followed by displacement with azide, enables equatorial hydroxyl groups to be converted into the related equatorial azides, axial hydroxyl group being unaffected253.Among other application of Mitsunobu chemistry are the synthesis of chroman-4-ones via aldol-Mitsunobu reactions254,the conversion of 0-ethers of benzylic secondary alcohols into esters255,an alternative route to 1-(primary of reversed azole n ~ c l e o s i d e sN~ -gly ~ ~ ,cosya1k y l ) b e n z o t r i a z ~ l e sthe ~ ~ ~synthesis , lated disymmetric fused heterocyclic systems258, thiofunctionalised pentof ~ r a n o s e s ~and ~ ~ ,a remarkable stereocontrolled fragmentation reaction in macrolide antibiotic chemistry260.The Staudinger reaction of tertiary phosphines with azido compounds has been applied in the synthesis of macrocyclic and cagelike compounds, e.g., 17726’3262. The reaction of a,o-diphosphines with an azide of a carbofunctional diarylthiophosphoric acid is the key step for the design of the core of an extended series of phosphorus-containing d e n d r i m e r ~Attack ~ ~ ~ . at only one of the phosphine functionalities in 1, 2-bis(diphenylphosphino)benzene (and cis- 1,2-bis(diphenyIphosphino)ethene) occurs in their reactions with a range of organic azides, giving phosphino-phosphazenes, e.g., 178264.

177 X

= 0 or

NH

178 R = MeSSi, pCNC6H4, PhCO or Ph2P(O)

23

1: Phosplzines and Pliosplzonium Salts

1.2.4 Miscellaneous Reactions of' Phosphines. - Gas phase pyrolysis of diallyl(4fluoropheny1)phosphine and allyl(t-buty1amino)phenylphosphine results in the formation of 1-(4-fluorophenyl)- 1-phosphabutadiene and 1-phenyl-2(tbutyl)iminophosphene, respectively, as the primary products, which then give rise to [4 + 21 and [2 + 21 cycloaddition products265. The phosphines 179 have been of the pyrazolate anion with prepared by the reaction tris(pentafluorophenyl)phosphine, para-substitution being proved by NMR and crystallographic studies266.Whereas insertion of a methylene group into a boronhydrogen bond occurs when tertiary phosphine-boranes are heated with a samarium carbenoid reagent, the related reaction of secondary phosphine-borane complexes proceeds with methylene insertion into the phosphorus-hydrogen bond267. Evidence for the formation of radical polycation species has been presented in the electrochemical oxidation of phosphines containing two or three tetrathiafulvalene moieties, e.g., 180268.The reactions of cation radicals generated from trivalent phosphorus compounds by y-irradiation or anodic oxidation have been reviewed269.

179

180

The chiral phosphine 181 has been resolved with the aid of a new chiral amine-palladium complex270. The tetraphosphine 182 has been separated into diastereoisomers, which have then been subsequently resolved27'. A chiral amine-palladium complex has also been used to resolve methylphenylbenzylp h ~ s p h i n e The ~ ~ ~ tetraphosphino-l,3-butadiene . 183 has been obtained (as a molybdenum carbonyl complex) from photolysis of molybdenum carbonyl complexes of 1,2-bi~-diphenylphosphinoethyne~~~. The phosphines 184 have been obtained from the reactions of diethyltrimethylsilylphosphine with a series of ben~ylideneindanones~~~. Factors affecting the basicity of phosphines continue to attract the attention of the theoreticians2757276. The tetraphosphacubane system 185 has been shown to act as an unprecedentedly strong base in the gas phase, but not in solution277. A theoretical study of the reactivity of the tetraphosphacubane system has also appeared278. Dimethylamino-substituted triarylphosphines exhibit dual fluorescence in polar solv e n t ~ Solution ~ ~ ~ . studies of the conformation of the %membered ring system 186 have been reported280. Significant double bond character is reported to be present in the phosphorus-carbon bonds of triarylphosphines, according to the results of an ab-initio study28'. A new approach for estimating the effective steric impact of bulky tertiary alkylphosphine ligands has been developed282. The uses of trialkylphosphine complexes of rhodium as homogeneous catalysts have been reviewed283. X-Ray studies of chelating a,o-bis(dialky1phosphin0)alkanes (which are liquid at room temperature) have been carried out at low temperatures, and the structural data used to rationalise their

Orgunophosphorus Chemistry

24

I-,

Ph2PnP Ph2P

A

Ph 181

A

P

A

PPh2

(P~~P)~C=CH-CH=C(PP~Z)~

Ph 182

OSiMe3 *7H-&-R3

183

9

R2

PEt2

H R' 184 R ' = H o r M e R2 = H, CI or NO2 R3 = H or Me0

185 R = Me or But

. Ph 186

properties as l i g a n d ~ Sulfonation ~~~. of arylphosphines continues to be used as a strategy for the synthesis of water-soluble systems285, and the use of such ligands in rhodium-catalysed hydroformylation procedures has been reviewed286. Treatment of the monomeric ether-phosphine ligands 187 with tetraethoxysilane under sol-gel conditions has given a series of polysiloxanebound ether-phosphine l i g a n d ~ ~ The ' ~ . chiral phosphine 188 has been used as a ligand in a palladium-catalysed enantioseletive substitution reaction288. The phosphino-benzoate esters 189 have been subjected to a rhodium-catalysed stereoselective hydroformylation to give the phosphino-aldehyde 190289. Electrospray and Fourier Transform ion cyclotron resonance spectrometric techniques have been used to study the interaction of tris(2-cyanoethy1)phosphine with metal ions290.

2

(MeO)&i(CH2),P( Ph)CH&H20Me 187 n = 3 , 6 o r 8

PPh2

9

Me 189

qx

188

PPh2

190

1: Phosphines und Phosphonium Sults

2

25

Halogenophosphines

2.1 Preparation. - The new sterically crowded dichlorophosphine 191 has been prepared via the reaction of an aryllithium reagent with phosphorus trichloride. This dichlorophosphine serves as a precursor for the related phosphinic acid ArP(O)(OH)H, the primary phosphine ArPH2, and the diphosphene ArP=PAr29'. Interest continues in the direct halogenophosphonation of heterocyclic systems. Thus, treating N-methylpyrrole with phosphorus tribromide in pyridine gives initially the 2-dibromophosphino system 192. However, at room temperature, this rearranges to the 3-isomer 193, in almost quantitative yield292. Similarly, the reactions of N-alkylindoles with phosphorus trihalides also result in the formation of the 3-dihalogenophosphino-derivatives194293._,

Heterocyclic halogenophosphines, e.g., 195 have been isolated from the reactions of phosphonium ylides, bearing trimethylsilyl groups at the ylidic carbon, with phosphorus t r i h a l i d e ~ ~Related ~~. reactions with the ylide Ph3P=C(PC12)2 have given the 1,3-diphosphanaphthalenesystem 196, which, with gallium trichloride is converted into the lox-system 19'7, involving two coordinate phosphorus295. The functionalised halogenophosphines 198 have been prepared by the uncatalysed electrophilic addition of phosphorus trihalides to a l k o ~ y a c e t y l e n e s ~The ~ ~ .formation of an unstable intermediate phosphirenium halide in these reactions was also demonstrated297. 1-Alkylpyridinium bromides having an activated N-methylene group have been shown to react with phosphorus trichloride to give the (dichlorophosphinomethylene) pyridinium ylides 199, except where a more reactive 2(or 4)-alkyl substituent is present, when dichlorophosphonylated anhydrobases, e.g., 200, are formed preferen t iaiiy298. 2.2 Reactions. -- Organoiodophosphines, and phosphorus tri-iodide, have been shown to undergo equilibrium formation of phosphine-phosphonium dimers. The association may proceed further, and result in the formation of P-P bonds by elimination of iodine299. Certain diiodo(organo)phosphines also react with T H F to give tetraorganocyclotetraphosphines,1,6diiodobutane, and other prod u c t ~ Diorganophosphinic ~~~. iodides have been isolated from the reactions of 1adamantyl- and phenyl-diiodophosphine with 1-hydr~xyadamantane~".The

26

Orgunophosphorus Chemistry PPh3 X.pKp,X

A

Ph3P

PAPPh3 I

X 195

196 R’, R2= H or Me

198 R1 = H or alkyl R2 = alkyl X = CI or Br

197

199 R = C02R’ or COPh

200

reactions of 5-chlorodibenzophosphole 201 and di-r-butylchlorophosphine with aluminium chloride have been explored. The former gives rise to a P-P system 202, whereas, under the same conditions, the latter gives the simple salt [ButZ PCI2] A1C14302.The ylidyl substituent in the chlorophosphines 203 causes a significant lengthening of the phosphorus-chlorine bond, to the extent that, for R = Me2N, an ionic structure is considered to be present in dichloromethane solution303. P--P-bonded compounds, e.g., 204, have been isolated from the reactions of r-butyl(trimethylsily1)chlorophosphine with dicyclopentadienyldimethylzirconium in the presence of a copper(1) catalyst3w. A family of bis(trichlorosily1)phosphines (205) has been obtained from the reactions of

201

Ph3P=C,

202

Ph Me

BUi

P-CI

RI 203 R = Me or Me2N

/p-p:B”t

Me

204

SiCI3 R-P,

Sic13 205 R = But, l-adamantyl, (Me3Si)2CHor Pr12N

organodichlorophosphines with trichlorosilane or h e x a c h l o r ~ d i s i l a n eTreat~~~. ment of the isoprene-phosphorus trichloride adduct with magnesium or hexachlorodisilane gives the heterocyclic system 206, which, in the presence of an

I: Phosphines and Phosphonium Salts

27

excess of the above reagents is converted into the diphosphine 207,isolated as a mixture of diastereois~mers~~~. The phosphirane 208 has been isolated from the reaction of bis(pentamethylcyclopentadieny1)chlorophosphine with lithium bis(trimethylsily1)amide in refluxing hexane, and its reactions with dimethyl acetylenedicarboxylate and diethyl azodicarboxylate studied307.The triplet ground state phosphinyl diradical209 has been prepared by photoinduced dissociative electron capture by the related bisphosphinous chloride in the presence of an electron-rich alkene at 11OK3'*. A new route to free acylphosphines is promised by the isolation of acylphosphine-iron complexes from the reactions of lithium acyltetracarbonylferrates with chlor~diphenylphosphine~~~. New chiral phosphinous esters of a partially protected glucofuranose system have been obtained from the reactions of chiral diorganophosphines with a free alcohol group of the carbohydrate molecule310.Reactions with amino compounds have also been reported3". With 5-fluorouracil, chlorodiphenylphosphine gives the N-phosphino system 2lO3I2.Further studies of the reactions of diphenylphosphinous isocyanate with nitrilimines have also been reported3I3.

d Me'cp-pa Me

I CI 206

207

Me

+

209

3

208

I PPh2 210

Phosphine Oxides and Related Chalcogenides

3.1 Preparation. - A series of phosphetane oxides (211),bearing chiral groups at

phosphorus, has been prepared from the appropriate chiral dichlorophosphine in a standard synthetic procedure for the phosphetane system3I4.The related Pmenthylphosphetane oxide (21 1, R* = menthyl) can be metallated at the a-carbon using lithium tetramethylpiperidide, and subsequent treatment with a chlorosilane gives the chiral a-silylphosphetane oxide 212, which can be reduced to the A route to the menthylphosphetane related phosphine using trichl~rosilane~'~. sulfide 213 has been developed, and this can also be metallated and alkylated at the ~x-carbon~'~. Further development of synthetic routes to chiral 5-phenyldibenzophosphepin-oxide systems, e.g., 214 has been reported317.The phosphine oxide 215 undergoes metallation ortho to the diphenylphosphinoyl group on

28


treatment with lithium tetramethylpiperidide. Subsequent iodination and Ullmanii coupling has given the biphenylic diphosphine dioxide 21(i3I8. S II

Men-rl 21 1 R* = e.g. (S)-bornyl or (1 R)-isopinocamphenyl

212

213

K,

0

214

215

216

Chiral phosphine oxides 217 have been obtained in high enantiomeric purity by treatment of diastereoisomeric carbohydrate esters of methyl(pheny1)phosphinic acid with a Grignard reagent319. The optically-active phosphineborane 218 is oxidised to the phosphine oxide 219 ( X = O ) by m-chloroperbenzoic acid with almost complete retention of configuration at phosphorus. Oxidation of 218 with iodine in the presence of water occurred with inversion of configuration, again with high stereospecificity. With sulfur in the presence of N-methylmorpholine, the related phosphine sulfide 219 (X= S) is formed, again with the retention of c~nfiguration~~'. The course of the reaction of diphenylphosphine sulfide with dihaloalkanes depends on the length of the alkane chain, the nature of the halogen, and the conditions. With dihalomethanes, products are either the halomethylphosphine sulfide, or the reduction product diphenyl(methy1) phosphine sulfide. With 1,2-dibromoethane, ethylene is evolved and tetraphenyldiphosphinedisulfide is formed. Longer chain a,w-dibromoalkAl . route to the anes give the related a,w-alkylenediphosphine d i s ~ l f i d e s ~ ~ nitronylnitroxyl radical-substituted phosphine oxides 220 has been reported322. The phosphine oxide 221 is the stable product resulting from thermal isomerisation of the mixture of prototopic isomers formed in the reaction of Nbenzylarylimidoyl chlorides with ethyl diphenylph~sphinite'~~. The aminoalkylphosphine oxides 222 have been isolated from addition of diphenylphosphine to Addition of dimethylimines derived from 7-amino- 1,3,5-tria~aadamantane~~~. phosphine oxide to a C=N unit is the key step in the synthesis of the phosphine oxides 223325. A series of N-substituted (aminomethy1ene)diphenyIphosphine oxides has been obtained from the reaction of diphenylphosphine oxide, paraformaldehyde, and a secondary amine under modified Mannich conditions326.A route from the arylaminovinylphosphine oxides 224 to the quinolyl system 225 has been developed327.The enaminophosphine oxides 226 have been obtained by addition

I : Phosphines und Phosphonium Sults

29 0

218

217 R = eMeOC&l4 or Pr”

219

220

0 II

0 II R’NHCHR2PPh2

0 II Ph2P-CH-N=CHPh I Ar 221 Ar = m,pFC6H4

222 R’ = 1,3,5-triazaadarnant-7-~1 R2 = aryl

223

CF3

of amines to allenylphosphine oxides and subsequently reduced by hydride reagents to the aminoalkylphosphine oxides 227328.The reduction of a-alkyl-Pketophosphine oxides cg., 228 with lithium borohydride in the presence of titanium tetrachloride proceeds with high anti-diastereoselectivity to give the corresponding P-hydroxyalkylphosphine oxides, e.g., 229329.

224

R~NH

225 R’ = Me or OMe R2 = H, Me or ptolyl R3 = Ph or o-tolyl

o IPhp

R1&

227

226

0 0 II II Ph2PCH(Me)CPh

0 II Ph2PCH(Me)CH(OH)Ph

228

229

A diastereoselective preparation of or-hydroxyalkylphosphine oxides 230 is offered by the reaction of lithiated t-butyl(pheny1)phosphine oxide with carbonyl compounds330. The same group has also studied the reactions of the above lithiated secondary phosphine oxide with bis(haloalky1) reagents, which afford a series of doubly chiral diphosphine dioxide ligands, e.g., 23133’. Further progress in the synthesis of highly functionalised alkyldiphenylphosphine oxides has been reported by Warren’s group, much of it focused upon the reactions of a-lithiated alkyldiphenylphosphine oxides with e l e c t r o p h i l e ~ ~Support ~ ~ ‘ ~ ~ ~has . grown for the view that a-lithiated alkyldiphenylphosphine oxides are not configurationally Among new systems prepared by Warren’s group stable, even at -78°C3357336. are 232337933g, 233339,and 234340. The fluoroalkylphosphine oxides 235 are formed via a rearrangement process in the reactions of difluoroallylic alcohols with chlorodiphenylphosphine in the


30

230

232 R’ = H,OH, Me or Ph R2 = H, Me, Ph or OH

231

0

Ph2+ !

P h p ! v R HO Me

R’

OH 234 R’ = Me, Bu or Ph, R2 = H or Me

233 R = CHO or CH20H

presence of t r i e t h ~ l a m i n e ~A~ ’new . route to diphenylalkenylphosphine oxides is provided by the reactions of the diphenylphosphinoyl radical (obtained by treatment of diphenylphosphine oxide with a manganese(II1) complex) with alkenes. Thus, e.g., with dihydropyran, 236 is formed342.Several pyridyl(and 8quinoly1)oxymethylenephosphine oxides, e.g., 237 have been obtained via the reaction of chloromethyldimethylphosphine oxide with the sodium salts of hydroxypyridines and 8 - h y d r o ~ y q u i n o l i n e Intramolecular ~~~. cyclisation of the allenyldiphenylphosphine oxide 238 provides an efficient route to the dihydrofurylphosphine oxides 239344.The fl-ketophosphine chalcogenides 240 have been obtained from the reactions of enamines with chlorodiphenylphosphine in the presence of triethylamine, followed by treatment with oxygen, sulfur, or selenium, and then acidic hydrolysis345. Phosphine oxides bearing cyclopentenone groups, e.g., 241, have been prepared via the tandem reaction of C lithiated alkyldiphenylphosphazenes with dimethyl acetylenedicarboxylate and of difunctional phosphine oxides (242) has been m e t h ~ l r n a l e a t e ~A~ ~series . prepared and used as reactive monomers in the synthesis of fire-resistant po~yrners~~~-~~’. 0

0

OMEM

Php!*R’ F F 235 R’, R2 = H or Et

239 R = alkyl or aryl

0

a N

236

240 n = 0-2 or 7 X = 0, S or Se

On’’ 237

CH2CHp0SiMe2Bu‘

RCH=C=C

/

0

PPhp II

PMe2

0 238

241

242 R = Me or Ph X = NCO, NH2 or C0pH

31

I : Pliosphines unci Phosphonium Sults

Reactions. - On heating, the phosphine oxides 243 do not aromatise but undergo a series of rearrangements via diradical intermediates to form various The tetracyclic system’245 has been cyclised products, e.g., 244 and 2453517352. isolated as two thermally stable rotamers, as a result of completely hindered rotation about the ring-P(0)Ph2 bond353.A simpler, more efficient procedure has been developed for the conversion of the phosphabicyclo[3.1 .O]-hexane oxides 246 into the hexahydrophosphinine oxides 247, involving catalytic hydrogenolysis under pressure in the presence of a base354.The importance of the 3-phosphabicyclo [3.1.O]hexane-3-oxide system 246 as an intermediate for the synthesis of dihydro-, tetrahydro-, and hexahydro-phosphinines, and also phosphinines, has been reviewed355. Nucleophilic additions to the carbonyl group of 248 have provided a series of derivatives of this bicyclic system356. Enantioenrichment of the phospholane system 249 has been achieved by lithiation at a ring carbon adjacent to phosphorus, using butyllithium in the presence of (-)-sparteine, followed by p r ~ t o n a t i o n ~ ~ ~ . 3.2

244 R = B u ”

243 X = ptolyl or H R = Bun, Ph or Mes

245 Ar = ptolyl

H,

246 R = BuorPh

247

248 R = H o r P h , X = O o r S

249

The phosphine sulfide 250 has been prepared by the reaction of tris(ch1oromethy1)phosphine sulfide with sodium d i a l l y l i s ~ c y a n u r a t eBorylation ~~~. of 251 in the presence of 1,3,5-triazaadamantanes has given the salts 252 involving the 1,3,2,5-dioxaborataphosphorinane~ y s t e m ” ~A. regiospecific route to the dibenzo[b,e]phosphininone system 253 is provided by treatment of the phosphine oxide 254 with lithium diisopropylamide, the reaction being a new double anionic equivalent of the Friedel-Crafts reaction360. The reaction of N-methyl-Ntrimethylsilylaminomethyldimethylphosphine oxide (255) with various peptoid acyl chlorides has given a series of peptoids bearing organoaminomethyldimethylphosphine oxide The atropisomeric phosphine oxides 256 have been shown to racemise very rapidly in solution362.Tertiary phosphine oxides have been shown to act as nucleophilic catalysts in the aqueous hydrolysis of diphenyl of phosphorus-centred radicals chlorophosphate in a ~ e t o n i t r i l eThe ~ ~ ~formation . from acylphosphine oxide photoinitiators has been studied by 3’P-, 13C-, and

32


'

H-CIDNP and ESR technique^^^. A laser flash photolysis and time-resolved ESR study of the formation of phosphinoyl radicals from benzoyldiphenylphosphine oxide and 257 has appeared365. The addition of dialkylphosphoryi radicals to a fullerene system has also been Interest in adducts of phosphine oxides with proton donors, notably phenols3673368 and other solvcnt has continued. R

go

250 R = ally1

251 R = H or pCICsH4

d

252 R = H or pCICsH4 X = H, CI or NH2

0

O'/

\

253

256 R = H, Me or Tf

254

255

257 R' = OMe, R2 = 2,2,4-trimethylpentyI

3.3 Structural and Physical Aspects. - A theoretical approach (density functional theory) has been used to explore the nature of the phosphoruschalcogen bond in the species Me3P=E ( E = O , S, Se or Te; and also X = B H 3 , CH2, and NH) in terms of the relative strengths of 0- and x-bonding components. Down the group from oxygen to tellurium, the overall bond strength decreases from 544 kJmol-' to 184 kJmol-', but the x-bonding component becomes more significant with respect to the o-bond. For E = BH3, the phosphorus-boron bond energy is only 166 kJ mol-' 371. The first measurements of the enthalpies of combustion, sublimation, and fusion of triphenylphosphine sulfide have enabled estimates of its enthalpy of formation to be derived, the P=S bond enthalpy being 394 kJ mol-' 372. Dipole moment and infrared studies indicate that, in solution, the 2-(thiophosphoryl)-1,3-dithianes 258 exist mainly as an equilibrium mixture of two chair-like conformations in which the thiophosphoryl group is axially oriented373. In contrast, a solid state

33


crystallographic study of the related 2-(diphenylphosphinoy1)-1,3-dioxane 259 has shown that the phosphinoyl group occupies an equatorial position374. Structural studies of the related 5-membered ring systems 260 have shed light on solid state conformations and anomeric effects between ring sulfurs and phosphorus375. An understanding of the conformational properties of 2(hydroxypenty1)diphenylphosphine oxide (and its acetate) has been gained via a combination of solid state crystallographic, solution spectroscopic, and modelling A solution N M R and solid state crystallographic study has been reported for the C-lithiated phosphine oxide 261 in which the lithium ion is associated with the phosphoryl oxygen, and the (axial) carbanionic carbon is almost planar377. Among other structural studies of phosphine chalcog e n i d e ~ ~are~ those ~ ” ~ of ~ 262379,a series of 1-(hydroxya1kyl)dimethylphosphine sulfides380,and 263382.Electron impact mass spectra of several five- and sixmembered heterocyclic phosphine oxides, e.g., 264, reveal the loss of oxophosphene moieties ( R - P z O ) ~ ~The ~ . reactivity of the trimethylphosphine oxide radical cation has been investigated using ion-molecule reactions in a mass spectrometer384.

D

258 R’ = Me or Ph R2 = H or But

260 X

259

0

R 262 R = OCH2CH20Me

=

II Ph2PCH2CH2iMe31-

263

p

=

O

Li+(thf)2

261

0, S or Se

$‘ d’k 264 R = Ph or V

B

u

t

Me‘

3.4 Phosphine Chalcogenides as Ligands. - This remains an area of considerable activity. The coordination chemistry of the bidentate ligand systems 265385and has received attention. Complexes of macrocyclic phosphine oxides bearing a NS2PO donor set have been c h a r a c t e r i ~ e dDifferences ~~~. in the ability of the phosphinoyl centres in the unsymmetric vinylenediphosphine oxides 267 to complex with phosphorus pentafluoride have been studied by I9F N M R techniq u e ~ Complexes ~ ~ ~ . of triphenylphosphine oxide with ~ o p p e r ( I 1 and ) ~ ~ organo~ l a n t h a n ~ m ( I I 1 )acceptors ~~~ have been reported. Copper(I1) and cobalt(I1) complexes of polymer-supported triphenylphosphine oxide have also been characterised, and shown to absorb sulfur dioxide39’. Silver and gold complexes of polydentate thioether-phosphine chalcogenides e.g., 268 have been cha ract e r i ~ e d ~On ~ ~ . treatment with benzylmanganese-pentacarbonyl, triphenylphosphine-oxide, -sulfide and -selenide undergo cyclomanganation to form the

34


heterocyclic system 269393. Complexes of tetraalkyldiphosphine disulfides with metal carbonyl acceptors have been prepared by both photochemical and thermal routes3". Several groups have described complexes of phosphine sulfide and selenide ligands, both simple and chelating, with copper, silver and gold

acceptor^^^^-^^^.

265

266

267 R = Etor Ph

Ph, ,Ph

Ph2P II X

4

4.1

s 268

PPtl2 II X

Mn (CO)4 269 X = 0, S or Se

Phosphonium Salts

Preparation. - Conventional quaternization procedures have been used for the synthesis of a series of o-phenylalkyltrimethylphosphoniumsalts 270399, the and the triphosphonium salt 27I4Oo,the amidoalkylphosphonium salts 272401, tetraphosphonioporphyrin system 273402.Porphyrins bearing a meso-phosphonium substituent, e.g., 274, have been obtained from the reaction of the related trimethylammoniomethylporphyrin iodide with tertiary phosphines or diphosphines403.Electrochemical oxidation of zinc tetraphenylporphyrin in the presence of bis(dipheny1phosphino)ethyne (0.5 mol) leads to the formation of the pbridged dimer 27S4O4.The reaction of benzyl- and thienylmethyl-alcohols, bearing tertiary amino substituents, with triphenylphosphonium bromide, in dichloromethane, chloroform or acetonitrile, with azeotropic removal of water, provides an improved route to substituted (hetero)arylmethylphosphonium salts405.The silica bound 'two headed' (bicipital) bis(tetraary1phosphonium)salt 276 has been obtained via a conventional Horner approach via the related bromoarene, triphenylphosphine and either nickel(I1) bromide or palladium(I1) acetate. This system gives unusually high catalytic rate enhancements in some nucleophilic substitution reactions, suggesting cooperation between the neighbouring phosphonium centres406.A practical route to chiral and achiral phosphonium salts from tertiary phosphine-borane complexes has been developed, entailing the reaction of the complex with an alkyl halide in a 1-octene-THF solvent system. The phosphonium salt simply crystallises from the solvent as the reaction proceeds. Phosphine-boranes also react with aryl halides, but need the presence of nickel(I1) bromide as catalyst407. Coordination template-assisted

35

I : Phosphines und Phosphonium Sults

R

R

R

R

274 R = Me, Et or CH2CH2C02P$

275

278

0 +PPh3 B f

Q

36


nickel(I1)-catalysed formation of arylphosphonium salts has been employed in the synthesis of two series of phosphonium phenolate betaines, 277 and 278, which have been found to exhibit negative solvatochromism408. The phosphonium zwitterion 279 has been obtained from the reaction of triphenylphosphine with 2,3-dichloro-4-oxo-2-butenoic acid (or its esters), followed by treatment with triethylamine409. Treatment of l-acyl-Zbromoalkynes with triphenylphosphine has given the acylethynylphosphonium salts 2804'0. Polymers bearing phosphonium groups have been prepared from a l k ~ n y l - ~and ' p r ~ p a r g y l - ~phos'* phonium salts. The phosphonio-borato betaines 281 have been obtained from the reaction of simple ylides with dimethylaminobis(trifluoromethyl)borane4'3. Adducts of cyanomethylenetriphenylphosphorane with acyl-isocyanates and -thiocyanates undergo cyclisation with hydrogen chloride to form the salts 282, from which phosphonium betaines can be easily obtained4I4. Routes to heterocyclic betaines, e.g., 283, have also been developed4153416. The reaction of the tributylphosphine - carbon disulfide adduct with norbornene has given the zwitterion 284, which, in solution, dissociates to form the ylide 285 from which 2alkylidene-l,3-dithiolanescan be formed417. Treatment of trialkyphosphinecarbon disulfide adducts with the complex [Cpz ZrHCI], gives the reactive complex 286, from which phosphonium salts, e.g., 287, can be prepared by alkylation or a ~ y l a t i o n ~Improved '~. routes to the phospholenium salts 288 have been reported, and the reactions of this system with butyllithium and potassium t-butoxide studied4I9. The spirocyclic Meisenheimer complex 289 has been

oc"

aN=N

PR3

6Ph3

277 R = B u o r P h X = CI, Br, But or Ph

278 X = F, CI, Me or Ph

0

cl* Ph3P

0279

f:

Ph36-CH-B(CF3)2 I I R NMe2 281 R = H orMe

+

R-C-C=C-PPh3 Br 280 R = Ph or 2-thienyl

H

R 282 X = O o r S

Ph2C

H

H

283

284

H

285


37

isolated from the reaction of a 2,3-dihydroxypropylphosphoniumsalt with picryl fluoride420. Phosphonio-substituted-tetrahydro-1,3-diphosphinines and -tetrahydro- 1,2,6-azadiphosphinines, e.g., 290 have been prepared42’. Hexaalkylbisphosphonium salts [R3P-PR3I2+ 2X-, have been obtained from the electrochemical oxidation of trialkyphosphines, presumably via the reaction of an initially formed trialkylphosphonio cation radical with a second molecule of the phosphine, followed by an oxidation step422.A wide variety of phosphonium salts bearing unusual anions has also been described, including p o l y h a l i d e ~ ~ ~ ~ ~ fullerene radical anions4257426, s i l s e s q ~ i o x a n ea~ semiconducting ~~, complex thiol a t ~ n i c k e l a t eand ~ ~ ~the , triphenylmethanide ion429. R

B& ~ ~ ~ . OEt

fM(C0)5 (Me3Si)2C=P

@PH I

C ' = CHPh Etd 313 M = C r o r W

R 317 R = Me2N. Et2N, Pri2Nor But

318

PH 314

P

315

Me%Ge=C=PAr 319 Ar =2,4,6-But3C6H2

316

[But&CHSiMe3]AICld320

The influence of fluorine as a substituent at phosphorus in two coordinate P=C, P=Si, P=O and P=S systems has received theoretical consideration in connection with their rearrangement to three-coordinate phosphorus species494. The reactions of P=C and P=N systems with the complex [Cp2ZrHCI], have been reviewed495. The reactions of iminophosphenes with a zirconium-benzyne complex have also been investigated, leading to the isolation of new Zr, N, Pheterocyclic systems496.New P-aminoiminophosphene systems have been prepared497.The cycloadducts 321 are formed in the reactions of the iminophosphene CIP=NAr (Ar = 2,4 6 - B ~ ' 3C6H2) with dialkylarninoalkyne~~~~. Alkoxyand dialkylamino-triorganotincompounds have been shown to add to the phosphorus atom of P-dialkylaminoiminophospheneswith the formation of P-

42


stannylated i m i n o p h o s p h ~ r a n e sCrystallographic ~~~. and spectroscopic studies of iminophosphenes have also a ~ p e a r e d ' ~ - ~The ' ~ . first stable iminoarsene (322)has been c h a r a c t e r i ~ e d ~The ~ . chemistry of phospha- and arsa-silenes has been reviewed505.Sterically unhindered phospha-silenes, e.g., 323, have been obtained from the flash vapour phase thermolysis of cyclosilaphosphines506.Evidence has been provided of the formation of a phosphasilene bearing a complex metallosubstituent at pho~phorus~'~. CI,

Rr

R

NR2 321 Ar = 2,4,6-But3CeH2

Ar-As=N-Ar 322 Ar = 2,4,6-(CF3)3C6H2

Me2Si=PR 323 R = But or Ph

A theoretical study of the intermediates involved in the formation of phosphapropyne from pyrolysis of vinylphosphirane has led to a new route to phosphaalkynes. Thus, pyrolysis of trimethylsilyl(1-phosphirany1)diazomethane has yielded Me3SiC = P, via an intermediate I-phosphiranylmethylene508. Regioselectivity in the [3 + 21 cycloaddition reaction between phosphaethyne and diazomethane has been studied by theoretical technique?, and further examples of reactions of this type described5". Cycloaddition of phospha-alkynes with silylenes has also been reported5". The primary phosphine 324 has been isolated The chemistry from the addition of diethylphosphite to t-b~tylphosphaethyne"~. of phospha-alkyne cyclotetramer systems has been reviewed5I3, and the first examples of platinum(I1) complexes of such cage systems described5I4.Aspects of the reactivity of coordinated phospha-alkynes have received further study5I5,and a remarkable metal-mediated double reduction of t-butylphosphaethyne to the complexed fluorophosphine 325 described5I6. Phosphorus-carbon-aluminium cage structures have been isolated from the reactions of kinetically stable phospha-alkynes with trialkylaluminium corn pound^^'^, and new phosphaborane systems have been obtained from the reactions of phospha-alkynes with polyhedral b o r a n e ~ ~ 'Further ~ ~ ~ ' ~studies . of iso-phospha-alkyne coordination chemistry have appeared520.The reactivity of the ion 326 has been explored5*'. 0

II [(EtO)qPj2C-But I PH2 324

Bu'CH~PHF 325

[Ar-N=P]' 326 Ar = 2,4,6-But3C6H2

The chemistry of phosphinidene and phosphenium systems continues to be an active area. The electronic configurations of vinylnitrene and vinylphosphinidene have been compared in a theoretical study, which predicts that both have triplet ground states522.A triplet ground state is also found for phenylphosphinidine, whose properties are very similar to those of methylph~sphinidene~~~. A theoretical consideration of factors affecting the singlet-triplet energy separation in phosphinidenes has concluded that the singlet state is favoured by substituents

43

1: Phosphines and Phosphoniurn Salts

having x-type lone pairs, e.g., dialkylamino and dialkylphosphino, whereas the triplet state is favoured by hyperconjugative substituents, e.g., alkyl, boryl, and ~ i l y 1 ~Phenylphosphinidene ~~. forms adducts on treatment with heterocyclic carbenes, which have been formulated either as phospha-alkenes, e.g., 327, or as The latter formulation is favoured by phosphinidene complexes, e.g., 328525,526. the observation that treatment of the adduct with borane results in the formation of a bis(borane) complex, e.g., 329, indicating the availability of two lone pairs at phosphorus527.The area of metal-complexed phosphinidenes (and related N and As systems) has been reviewed528,and a number of new systems d e ~ c r i b e d ~ ~ ~ - ~ ~ l The reactivity of metal-phosphinidene complexes with a l k y n e ~ ~and ’ ~ also with carbonyl corn pound^^^^-^^^, has been explored. The 6x-aromatic phosphenium salt 330 has been characterised. The related system in which the double bond is reduced behaves as a typical covalent c h l o r o p h ~ s p h i n eExamples ~~~. of phosphenium ions stabilised by intramolecular N -+P coordination, e.g., 331 have been d e s ~ r i b e d ~ ~The ~ * chemistry ~~*. of ylidic 4n-4-membered ring systems, e.g., 332 has been reviewed539, and new studies of their synthesis and reactivity reported540754’.Further studies have also been reported of other phosphenium systems involving ylidyl s u b s t i t ~ e n t s ~and ~ ~ ,also ~ ~ ~the , ‘phosphinophosphinidene-phosphoranes’ 333544.

Mes

Mes

I

I Mes

I

I

Mes

327

Ph

I Mes

328

331 R

=

H or Ph

332

329

330

333

Further progress has been reported in the chemistry of cr3h5-p,-bonded systems. Full details of such systems stabilised by intramolecular coordination, as in, e.g., 334, have been described545.The kinetically stable system 335 has been prepared and its solid state structure determined546.The P-halobis(imino)-03hSphosphoranes 336 have also been prepared547, and detailed NMR studies of bis(imino) phosphoranes reported548.Quin’s group has continued studies of the generation and characterisation of reactive c ~ ~ ~ ~ - s y s t ee.g., m s , 337549-55I Methods for the generation of monomeric metaphosphate esters in solution have been investigated552. A theoretical approach has been used to probe the ~~~. mechanism of the reaction between phosphanylnitrenes 338 and b ~ r a n e s The thiophosphonic anhydride 339 behaves as a source of the dithioxophosphorane

44

Orgcrnophosphorus Chemistry

340, trappable with suitable dienes. Thus, e.g., on heating 339 with norboranadiene at 80 OC, the 1,2-thiaphosphetane 341 is formed554.

NAr

?\

(Me3Si)3C- /,FH2

ArN=P'

NMes* 334 X = S o r S e CR2 = CH2, CMe2

335 Mes* = 2,4,6-But3C6H2

n = 1-3

337

6

339 Fc = ferrocenyl

338

I X

336 Ar = 2,4,6-But3C~H2 X = CI, Bror I

340

341

Phosphirenes, Phospholes and Phosphinines

A study of the reactivity of I-chloro-1H-phosphirenes 342 with nucleophiles has shown that the chlorine is easily replaced555. A b initio calculations suggest that 1H-phosphirenes invert their configuration at phosphorus by a rotation of the PX group above the C2 moiety, rather than by the more usual trigonal inversion pathway involving a C*,-transition state556.Related calculations on the aromaticity of 1H-phosphirenium cations 343 have shown that the (T*ABMO associated with the P-X bond acts like an empty p - ~ r b i t a l ~A~ facile ~. route to the phosphirenium salts 344 is afforded by the reaction of the phosphiranium salt 345 with a l k y n e ~ ' ~The ~ . Pv-azaphosphirene system 346 has been obtained from the reaction of an iminophosphene with terminal a l k y n e ~ ~ ~ ~ .

342

343 R1 = Ph, But or 1-adamantyl R2 = alkyl X = F, CI, Br or I

OTfP t f Me 345

I?\

344 R1, R2 = Me or Ph

But NR2 346 R' = Bu, But, Et2NCH2,MeOCH2 or Me02C R2 = 2,4,6-But&H2

45

I : Phosphines and Phosphonium Sults

Activity in the phosphole area continues at a high level. The reaction of 2,3dimethylbutadiene with phenyldibromophosphine at 0 OC, followed by treatment with a-picoline, has given I-phenyl-3,4-dimethylphosphole(347) as the principal product, together with the bis(oxide) 348.The latter also forms on air-oxidation of the phosphole 347560.Routes have also been developed to the phospholes 349 which bear a bulky exocyclic phosphorus substituent. Structural studies reveal that the usual pyramidal configuration at phosphorus is significantly flattened, suggesting an enhancement of aromatic delocalisation in the phosphole ring. Reactivity studies of 349, (R = But) have shown that the ring, normally resistant to electrophilic substitution, undergoes Friedel-Crafts acylation to give 350 as the main product. The corresponding oxides of 349, as expected, behave as very reactive cyclic dienes, readily dimeri~ing~~'-'@.

4

d'

.

d C O M e

I

Ph 347

348

349 R = M e o r B u t

350

A stereochemical study has shown that the diphosphole 351 (having both axial chirality and chiral phosphorus atoms) can be separated by chromatography into diastereoisomeric diphosphole sulfides. These have then been reconverted into the parent diastereoisomeric diphospholes, which have been shown to re-equilibrate ~~. in solution565. Metal complexes of 351 have also been ~ h a r a c t e r i s e d ~The reactions of phospholide anions with halogenophosphines have been used to e.g., 352s68,which shows no unusual prepare P-phosphinopho~pholes,~~~~~~~ structural features. Routes to a-functionalised phospholide anions, e.g., 353, have been developed, such reagents having potential as building blocks for the synthesis of phosphorus analogues of porphyrin macrocyclic systems5697570. An efficient route to the 2-phosphinophosphindoles 354 has also been described, involving a zirconocene-benzyne intermediate57'. A similar approach has also been used in the synthesis of the fused system 355572. A theoretical study of the Diels-Alder reactions between 1,3-butadiene and, respectively, cyclopentadiene and 2H-phosphole, has revealed a remarkable similarity between the two reactions573. Further studies of photocycloaddition reactions of phosphole moieties have also been reported574. Transition metal complexes of phospholide anions continue to attract attention575, and in particular the chemistry of phosphaferrocene systems remains a major i n t e r e ~ t ~ ~ ~ - ~ ~ The past year has also seen significant activity in the chemistry of di- and triphospholes, related polyphospholide anions, and also heterodiphosphole systems. Routes have been developed to the diphosphonio- 1,2-diphospholes 356,

46


352

351

354 R'

= Ph or

But, R2 = H or Ph

353 X = Ph, 2-pyridyl or C02Et

355

a cyclic 6n-system showing considerable flattening of bond angles at the 03phosphorus atom580,the diphosphonio- 1,2,4-triphospholide salts 35758 and the 2-diphenylphosphino-1,3-diphospholides358582.Examples of polyphosphaferrocenes derived from di- and tri-phospholide anions have been Further studies of the [4 + 21 cycloaddition reactions of 1,3-diphospholes and 1,2,4-triphosphoIes have also been reported58s.The synthesis and reactivity of the sterically crowded 1,2,4-triphosphoIe 359 has been explored, this system exhibiting an enhanced degree of aromaticity compared with simple p h o s p h ~ l e s ~ ~ ~ ~ ~ A route to the 1,4,2-diphosphastiboIidesalt 360 has been described588,together with its use in forming a variety of polyheterornetallo~enes~~~-~~', and a new phosphorus-antimony c a g e - ~ y s t e m ~ Routes ~ ~ . to the thia- and selena-diphospholes 361 have also been d e ~ c r i b e d ~Once ~ ~ .again, ~ ~ ~ there . has been significant activity in the area of azaphosphole ~ h e m i s t r y ' ~ ~including - ~ ~ ~ , the synthesis of the dipolar system 362602and the 1,2,3,4-diazddiphospholidesalt 363603.Also of interest are the results of ab-initio calculations on 1,3,2-diazaphospholes and the related 1,3,2-diazaphospholeniumion 364,which show that the latter is significantly delocalised, with an aromaticity comparable to pyrrole604. Two groups have reported theoretical studies of pentaphosphole (365). In contrast to the parent system of phosphole (C4H4PH), pentaphosphole is apparently planar, with a larger aromatic delocalisation energy605. Nevertheless, several possible Diels-Alder type dimeric forms were found to be significantly more stable than 365, and since it is not possible to introduce a stabilising substituent at one of the o*-phosphorus atoms, the likelihood of a successful synthesis of this system is smaPo6. A new route to the phosphinine system is provided by the rearrangement of 1alkynyl- 1,2-dihyrophosphetes 366, giving the substituted phosphinines 367607. Phosphinines bearing dialkylboryl groups, e.g., 368, have been obtained by the reactions of 3-dialkylborylstannoles with phospha-alkynes6". Interest has also continued in the coordination chemistry of p h o s p h i n i n e ~ ~ ~including ~ - ~ ' ~ , that of the new ligand system 3696'4. The 1,3,2-diazaphosphinine 370 is a versatile precursor to other phosphinine systems, undergoing stepwise addition-elimination reactions on heating with alkynes in toluene to give, respectively, the 1,2azaphosphinines 371 and the phosphinines 3726'5. The Diels-Alder reaction '

47

1: Phospliines and Phosphonium Suits

Ph

6Ph3

Ph36*P

2OTf-

R 356 R = Me or Ph

PPh2 358 R’ = Ph or Et R2 = Ph, Et or But

357 X = ha1 or Mes

x

R I CH(SiMe3)2 359

362

361 X = S, R = 1-adamantyl X = Se, R = But or Np

360

363

364

365

between 1,3,5-triphosphabenzene and phospha-acetylene to yield tetraphosphabarrelene has been examined by theoretical techniques, and compared with the carbon analogue between benzene and acetylene616. The reactivity of ring substituents in the 1,3-h5-diphosphinine system has also been

366 R’ = Ph or CsH13 R2 = Ph or Et

369

367

370

368

371

372

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I: Phosphines und Phosphonium Sults 100 101

102 I03 104 105 106 107 I08 I09 110

111

112 113 1 I4 1 I5 1 I6

1 I7 118 119 120 121 122 123 I24 125 I26 I27 128 129 130

51

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52 131 132 133 134 135 136 137 138 139 140 141 142 143 144 145 146 147 148 149 150 15 1 152 153 154 155 I56 157 158 159 160

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I : Phosphines and Phosphonium SuIts 162 163 164 I65 166 167 168 169 170 171 172 173 174 175 176 177 178 179 I80 181

182 183 184 I85 186 187 I88 I89 I90 191 I92 I93

53

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54 194 195 196 197 198 I99 200 20 1 202 203 204 205 206 207 208 209 210 21 1 212 213 214 215 216 217 218 219 220 22 1 222 223 224 225

Orgunophosphorus Chemisrry

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55

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56 260 26 1 262 263 264 265 266 267 268 269 270 27 1 272 27 3 274 275 276 277 278 279 280 28 1 282 28 3 284 285 286 287 288 289 290 29 1 292 293

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I : Pliosphines und Phosphonium Sults

294 29 5 296 297 298 299 300 30 1 302 303 304 305 306 307 308 309 310

31 1 312 31 3 314 31 5 316 317 318 319 320 32 1 322

57

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I : Phosphines and Phosphonium Sults

474 475 47 6 477 47 8 479 480 48 I 482 483 484 48 5 486 487 488 489 490 49 I 492 493 494 495 496 497 498 499 500 50 I

63

M. van der Sluis, V. Beverwijk, A. Termaten, E. Gavrilova, F. Bickelhaupt, H. Kooijman, N. Velman and A. L. Spek, Orgunometullics, 1997, 16, 1 1 4 4 . R. Pietschnig, E. Niecke, M. Nieger and K. Airola, J. Orgunomet. Chem., 1997, 529, 127. J. Grobe, D. Le Van, J. Winnemoller, B. Krebs and M. Laege, Z. Nuturforsch., B: Chem. Sci., 1996,51, 778. R. Streubel, M. Hobbold, J. Jeske and P. G. Jones, Angeto. Chem., Int. Ed. Engl., 1997,36, 1095. P. M. Warner, J. Org. Chem., 1996,61,7192. U. Salzner, S. M. Bachrach and D. C. Mulhearn, J. Comput. Chem., 1997, 18, 198. U. Salzner and S. M. Bachrach, J. Orgunomet. Chem., 1997,529, 15. M. T. Nguyen, A. Van Keer and L. G. Vanquickenborne, Chem. Ber.lReceui1, 1997, 130,69. J. Grobe, D. Le. Van, B. Broschk, M. Hegemann, B. Luth, G. Becker, M. Bohringer and E-U. Wurthwein, J. Orgunomet. Chem., 1997,529, 177. P. Binger, S. Leininger, M. Regitz, U. Bergstrasser, J. Bruckmann and C. Kruger, J. Orgunomet. Chem., 1997,529,2 I 5. H. Ramdane, H. Ranaivonjatovo, J. Escudie, S. Mathieu and N. Knouzi, Orgunometullics, 1996, 15, 3070. M-A. David, J. B. Alexander, D. S. Glueck, G. P. A. Yap, L. M. Liable-Sands and A. L. Rheingold, Orgunometallics, 1997, 16, 378. Yu. A. Veits, E. G. Neganova and I. P. Beletskaya, Zh. Org. Khim., 1996, 32, 1570 (Chem. Abstr., 1997,126, 3 17 429). M. Chentit, H. Sidorenkova, A. Jouati, G. Terron, M. Geoffroy and Y. Ellinger, J. Chem. Soc., Perkin. Trans. 2, 1997,921. A. Alberti, M. Benaglia, M.A. Della Bona, M. Guerra, A. Hudson and D. Macciantelli, Res. Chem. Intermed, 1996, 22, 381. J. Thomaier, G. Alcaraz, H. Grutzmacher, H. Hillebrecht, C. Marchand and U. Heim, J. Orgunomet. Chem., 1997,535,91. L. Weber, J-M. Quasdorff, H-G. Stammler and B. Neumann, 2. Anorg. Allg. Chem., 1996,622, 1935. L. Weber, 0. Kaminski, B. Quasdorff, H-G. Stammler and B. Neumann, J. Orgunomet. Chem., 1997,529,329. R. B. Bedford, A. F. Hill, C. Jones, A. J. P. White, D. J. Williams and J. D. E. T. Wilton-Ely, Chem. Commun., 1997, 179. H-P. Schrodel, A. Schmidpeter and H. Noth, Heterout. Chem., 1996,7, 355. M. T. Nguyen, A. Van Keer and L. G. Vanquickenborne, J. Organomet. Chem., 1997,529, 3. J-P. Majoral, M. Zablocka, A. Igau and N. Cenac, Chem. Ber., 1996,129,879. L. Dupuis, N. Pirio, P. Meunier, B. Gautheron, A. Mahieu, A. Igau and J-P. Majoral, Bull. Soc. Chim. Fr. , 1996,6 1 1. G. Schick, A. Loew, M. Nieger and E. Niecke, Heteroat. Chem., 1996,7,427. A. D. Averin, N. V. Lukashev, A. A. Borisenko, M. A. Kazankova and I. P. Beletskaya, Zh. Org. Khim., 1996,32,425 (Chem. Abstr., 1996, 125, 301 083). D. Hanssgen, T. Oster and M. Nieger, J. Orgunomet. Chem., 1996,526, 59. A. N. Chernega, A. A. Korkin and V. D. Romanenko, Zh. Obshch. Khim., 1995,65, 1823 (Chem. Abstr., 1996, 125, 10973). N. Poetschke, M. Nieger and E. Niecke, Actu Chem. Scund, 1997,51,337.

64 502 503 504 505 506 507 508 509 510 51 1

512 513 514 515 516 517 518 519 520 52 1 522 523 524 525 526 527 528 529 530 53 1

Orgunophosphorus Chemistry N. Burford, J. A. C. Clyburne, D. Silvert, S. Warner, W. A. Whitla and K. V. Darvesh, Inorg. Chem., 1997,36,482. D. Gudat and E. Niecke, Fresenius’ J. Anal. Chem., 1997,357,482. J-T. Ahlemann, A. Kunzel, H. W. Roesky, M. Noltemeyer, L. Markovskii and H-G. Schmidt, Inorg. Chem., 1996,356644. M. Driess, A h . Orgunomet. Chem., 1996,39, 193. V. Lefevre, J. L. Ripoll, Y. Dat, S. Joanteguy, V. Metail, A. Chrostowska-Senio and G . Pfister-Guillouzo, Organometallics, 1997, 16, 1635. M. Driess, H. Pritzkow and U. Winkler, J. Orgunomet. Chem., 1997,529, 3 13. D. J. Berger, P. P. Gaspar, P. Le Floch, F. Mathey and R. S. Grev, Organometullics, 1996,15,4904. L. Nyulaszi, P. Varnai, W. Eisfeld and M. Regitz, J. Comput. Chem., 1997, 18, 609. J. Grobe, D. LeVan, F. Immel, B. Krebs and M. Llge, Chem. Ber., 1996,129, 1271. R. Okazaki, Pure Appl. Chem., 1996,68,895. 1. I. Patsanovskii, V. I. Galkin, E. V. Popova, E. A. Ishmaeva, R. M. Aminova, K. Myuller and R. Schmutzler, Zh. Obshch. Khim., 1996, 66, 522 (Chem. Abstr., 1997,126, 8221). A. Mack and M. Regitz, Chem. Ber.lReceui1, 1997,130, 823. V. Caliman, P. B. Hitchcock, C. Jones and J. F. Nixon, Phosphorus, Sulfur, Silicon, Relut. Elem., 1996, 113, 15. R. B. Bedford, A. F. Hill, C. Jones, A. J. P. White, D. J. Williams and J. D. E. T. Wilton-Ely, J. Chem. Soc., Dulton Truns., 1997, 139. R . B. Bedford, D. E. Hibbs, A. F. Hill, M. B. Hursthouse, K. M. A. Malik and C. Jones, Chem. Commun., 1996, 1895. A. Hoffmann, B. Breit and M. Regitz, Chem. Ber.lReceui1, 1997,130,255. R. W. Miller and J. T. Spencer, Polyhedron, 1996, 15, 3151. R. W. Miller and J. T. Spencer, Orgunometullics, 1996, 15,4293. L. Weber, I. Schumann, M. H. Scheffer, H. G. Stammler and B. Neumann, Z. Nuturforsch., B: Chem. Sci., 1997,52,655. N. Burford, T. S. Cameron, J. A. C. Clyburne, K. Eichele, K. N. Robertson, S. Sereda, R. E. Wasylishen and W. A. Whitla, Inorg. Chem., 1996,35, 5460. V. Parasuk and C. J. Cramer, Chem. Phys. Lett., 1996,260, 7. M. T. Nguyen, A. Van Keer, L. A. Eriksson and L. G. Vanquickenborne, Chem. Phys. Lett., 1996, 254, 307. M. T. Nguyen, A. Van Keer and L. G. Vanquickenborne, J. Org. Chem., 1996, 61, 7077. A. J. Arduengo, H. V. R. Dias and J. C. Calabrese, Chem. Lett., 1997, 143. A. J. Arduengo, J. C. Calabrese, A. H. Cowley, H. V. R. Dias, J. R. Goerlich, W. J. Marshall and B. Riegel, Inorg. Chem., 1997,36, 21 51. A. J. Arduengo, C. J. Cannalt, J. A. C. Clyburne, A. H. Cowley and R. Pyati, Chem. Commun., 1997,981. A. K. Rodi, H. Ranaivonjatovo, J. Escudie and A. Kerbal, Muin Group Metd Chem., 1996,19, 199. D. Fenske and F. Simon, Angew. Chem., Int. Ed Engl., 1997,36,230. D. S . J. Arney, R. C. Schnabel, B. C. Scott and C. J. Burns, J. Am. Chem. Soc., 1996, 118,6780. R. Bartsch, A. J. Blake, B. F. G. Johnson, P. G. Jones, C. Muller, J. F. Nixon, M. Nowotny, R. Schmutzler and D. S. Shephard, Phosphorus, Sulfur, Silicon, Relut. Elem., 1996, 115, 201.


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H. Lang, M. Winter, M. Leise, L. Zsolnai, M. Buchner and G. Huttner, J. Orgunomet. Chem., 1997,533, 167. Y. Inubushi, N. H. T. Huy and F. Mathey, Chem. Commun., 1996, 1903. Y. Inubushi, N. H. T. Huy, L. Ricard and F. Mathey, J. Orgunornet. Chem., 1997, 533,83. R. Streubel, A. Ostrowski, H. Wilkens, F. Ruthe, J. Jesk and P. G. Jones, Angeiv. Chem., Int. Ed. Engl., 1997, 36, 378. M. K. Denk, S. Gupta and R. Ramachandran, Tetrahedron. Lett., 1996,37,9025. F. CarrC, C. Chuit, R. J. P. Corriu, A. Mehdi and C. Reye, J. Organomet. Chem., 1997,529, 59. J-P. Bezombes, F. Carri, C. Chuit, R. J. P. Corriu, A. Medhi and C. Reye, J. Orgunornet. Chem., 1997,535,81. L. Weber, Angew. Chem., Int. Ed. Engl., 1996,35,2618. M. Sanchez, R. RCau, F. Dahan, M. Regitz and G. Bertrand, Angew. Chem., Znt. Ed. Engl., 1996,35, 2228. H. H. Karsch, E. Witt and F. E. Hahn, Angeiv. Chem., Int. Ed. Engl., 1996,35,2242. A. Schmidpeter, G. Jochem, C. Klinger, C. Rob1 and H. Noth, J. Orgunornet. Chem., 1997,529, 87. D. Gudat, M. Nieger and M. Schrott, Inorg. Chem., 1997,36, 1476. I. Kovacs, E. Matern, E. Sattler and G. Fritz, Z. Anorg. Allg. Chem., 1996, 622, 1819. M. Yoshifuji, S. Sangu, K. Kamijo and K. Toyota, Chem. BerJReceuil, 1996, 129, 1049. B. Schinkels, A. Ruban, M. Nieger and E. Niecke, Chem. Commun., 1997,293. V. D. Romanenko and V. L. Rudzevich, Zh. Obshch. Khim., 1996, 66, 694 (Chem. Abstr., 1996, 125, 276 016). D. Gudat, E. Niecke, A. Ruban and V. von der Goenna, Mugn. Reson. Chem., 1996, 34,799. G. S. Quin, S. Janowski and L. D. Quin, Phosphorus, Sulfur, Silicon, Relnt. Elem., 1996, 115, 93. S. Jankowski, L. D. Quin, P. Paneth and M. H. O’Leary, J. Orgunornet. Chem., 1997, 529, 23. G. Keglevich, K. Ludanyi and L. D. Quin, Heteroal. Chem., 1997,8, 135. M. R. Banks, I. Gosney, D. Kilgour, J. I. G. Cadogan and P. K. G. Hodgson, Heterout. Chem., 1996,7, 503. M. T. Nguyen, A. Van Keer and L. G. Vanquickenborne, Inorg. Chem., 1996, 35, 41 85. M. R. StJ. Foreman, A. M. Z. Slawin and J. D. Woollins, Chem. Comrnun., 1997, 855.

555 556 557 558 559 560

65

H. Heydt, M.Ehle, S. Haber, J. Hoffmann, 0. Wagner, A. Goller, T. Clark and M. Regitz, Chem. Ber.lReceui1, 1997, 130, 71 1. A. Goller and T. Clark. Chem. Commun., 1997, 1033. A. Goller, H. Heydt and T. Clark, J. Org. Chem., 1996,61,5840. D. C. R. Hockless, M. A. McDonald, M. Pabel and S. B. Wild, J. Organomet. Chem., 1997,529, 189. A. D. Averin, N. V. Lukashev, A. A. Borisenko, M. A. Kazankova and I. P. Beletskaya, Zh. Org. Khim., 1996,32, 433 (Chem. Abstr., 1995, 125,301 084). J. Leis, K. Pihlaja and M. Karelson, Zh. Org. Khim., 1996, 32, 446 (Chem. Abstr.. 1996,125,301 085)

66 56 1 562 563 564 565 566 567 568 569 570 57 I 572 573 574

575 576 577

578 5 79 580 58 1 582 583 584 585 586 587 588

Orgunopirosphorus Chemistry

L. D. Quin, G. Keglevich, A. S. Ionkin, R. Kalgutar and G. Szalontai, J. Org. Chem., 1996,61,7801. L. Nyulaszi, G. Keglevich and L. D. Quin, J. Org. Chem., 1996,61, 7808. G. Keglevich, L. D. Quin, Z. Bocskei, G. M. Keseru, R. Kalgutkar and P. M. Lahti, J. Orgunomet. Chem., 1997,532, 109. G . Keglevich, Z. Bocskei, G. M. Kererii, K. Ujszaszy and L. D. Quin, J. Am. Chem. Soc., 1997, 119, 5095. 0. Tissot, M. Gouygou, J-C. Damn and G . G. A. Balavoine, Chem. Commun., 1996,2287. M. Gouygou. 0. Tissot, J-C. Daran and G. G . A. Balavoine, Orgunometullics, 1997, 16, 1008. D. Schmidt, S. Krill, B Wang, F. R. Fronczek and K. Lammertsma, J. Orgunomet. Chem., 1997,529, 197. A. H. Cowley, S. M. Dennis, S. Kamepalli, C. J. Carrano and M. R. Bond, J. Orgunomet. Chem., 1997,529,75. S. Tloland, M. Jeanjean and F. Mathey, Angew. Chem., Int. Ed Engl., 1997, 36, 98. B. Deschamps and F. Mathey, Bull. Soc. Chim. Fr., 1996,541. Y. Miquel, A. Igau, B. Donnadieu, J. P. Majoral, L. Dupuis, N. Pirio and P. Meunier, Chem. Cummun., 1997,279. M. Zablocka, N. Cenac, A. Igau, B. Donnadieu, J-P. Majoral, A. Skowronska and P Meunier Organometullics, 1996, 15, 5436. S. M. Bachrach and L. M. Perriott, Cun. J. Chem., 1996,74,839. €I. Ji, J. H. Nelson, A. DeCian, J. Fischer, B. Li, C. Wang, B. McCarty, Y. Aoki, J. W. Kenny, L. Solujic and E. B. Milosavljevic, J. Orgunornet. Chem., 1997, 529, 395. T. Arliguie, M. Ephritikhine, M. Lance and M. Nierlich, J. Orgunomet. Chem., 1996, 524,293. P. B. Hitchcock, G. A. Lawless and I. Marziano, J. Orgunomet. Chem., 1997, 527, 305. R. Bartsch, S. Datsenko, N. V. Ignatiev, C. Miiller, J. F. Nixon and C. J. Pickett, J. Organumet. Chem., 1997,529, 375. C. E. Garrett and G. C. Fu, J. Org. Chem., 1997,62,4534. A. Dupois, M. Gouygou, J-C. Daran and G. G . A. Balavoine, Bull. Soc. Chim. Fr., 1997,357. G. Jochem, H. Noth and A. Schmidpeter, Chem. Ber., 1996, 129,1083. H. P. Schrodel, A. Schmidpeter, TI, Noth and M. Schmidt, 2. Nuturforsch., B: Chem. Sci., 1996, 51, 1022. C. Charrier, N. Maigrot and F. Mathey, J. Orgunomet. Chem., 1997,529,69. C. Mueller, R. Bartsch, A. Fischer, P. G. Jones and R. Schmutzler, J. Orgunomet. Chem., 1996,512, 141. D. Boehm, F. Heinemann, D. Hu, S. Kummer and U. Zenneck, COIL Czech. Chem. Cummun., 1997,62, 309. V. Caliman, P. B. Hitchcock and J. F. Nixon, J. Orgunomef. Chem., 1997, 536-537, 273. V. Caliman, P. B. Hitchcock, J. F. Nixon and N . Sakarya, Bull. Soc. Chim. Belg., 1996,105,675. P. B. Hitchcock, J. F. Nixon and N. Sakarya, Chem. Cummun., 1996,2751. M. D. Francis, D. E. Hibbs, M. B. Hursthouse, C. Jones and K. M. A. Malik, J. Orgunornet.. Chem., 1997,527,291.

I : Phosphines uncl Phosphonium Sults 589 590 59 1 592 593 594 595 596 597 598 599 600 60 1 602 603 604 605 606 607 608 609 610 61 1 612 61 3 614 61 5 616 61 7

67

M. D. Francis, D. E. Hibbs, M. B. Hursthouse, C. Jones amd K. M. A. Malik, Chem. Commun., 1996, 1591. S . J. Black and C. Jones, J. Orgunomel. Chem., 1997,534,89. S . J. Black, M. D. Francis and C. Jones, J. Chem. SOC.,Dalton Truns., 1997,2183. S. J. Black, M. D. Francis and C. Jones, Chem. Commun., 1997,305. E. Lindner, E. Bosch, C. Maichle-Mossmer and H. Abram, J. Orgunomet. Chem., 1996,524, 67. M. Regitz and S. Krill, Phosphorus, Sulfur, Silicon, Relut. Elem., 1996,115,99. B. Manz, U. Bergstrasser, J. Kerth and G. Mass, Chem. Ber.lReceui1, 1997, 130, 779. B. Manz and G Mass, Tetruheclron, 1996,52, 10053. N. G. Khusainova, T. A. Zyablikova, R. G. Reshetkova and R. A. Cherkasov, Zh. Obshch. Khim., 1996,66,416 (Chem. Abstr., 1996,125,328 935). A. M. Kibardin, T. V. Gryaznova, A. N. Pudovik and V. A. Naumov, Zh. Obshch. Khim., 1996,66, 1455 (Chem. Abstr., 1997,126, 171 653. G. Baccolini, A. Munyaneza and C. Boga, Tetruheclron, 1996,52, 13 695. S. V. Chapyshev, U. Bergstrasser and M. Regiti, Khim. Geterotsikl. Soedin., 1996,67 (Chem. Abstr., 1996, 125, 168 160). A. Schmidpeter, F. Steinmuller and H. Noth, Chem. Ber., 1996,129, 1493. H-P. Schrodel and A. Schmidpeter, Chem. Ber.lReceui1, 1997, 130,89. C. Charrier, N. Maigrot, L. Ricard, P. Le. Floch arid F. Mathey, Angew. Chem., Znt. Ed. Engl., 1996,35, 2133. R. R. Sauers, Tetruhedron, 1997,53,2357. M. N. Glukhovtsev, A, Dransfield and P. von R. Schleyer, J. Phys. Chem., 1996, 125,168 141. L. Nyulaszi, Inorg. Chem., 1996,35,4690. N. Avarvari, P. Le Floch, C. Charrier and F. Mathey, Heferouf.Chem., 1996,7,397. B. Wrackmeyer and U. Klaus, J. Organomet. Chem., 1996,520,21 1. K. Waschbusch, P. Le Floch, L. Ricard and F. Mathey, Chem. Ber.lReceui1, 1997, 130,843. P. Le Floch, L. Ricard and F Mathey, Bull. SOC.Chim. Fr., 1996,691. P. Le Floch, S. Mansuy, L. Ricard, F. Mathey, A. Jutand and C. Amatore, Orgunometallics, 1996, 15, 3267. P. L. Arnold, F. G. N. Cloke, K. Khan and P. Scott, J. Organomef. Chem., 1997, 528,77. P. L. Arnold, G. N. Cloke and P. B. Hitchcock, Chem. Commun., 1997,481. B. Breit, Chem. Commun.,1996, 2071. N. Avarvari, P. Le Floch and F. Mathey, J. Am. Chem. Soc., 1996,118, 11978. S. M. Bachrach and P. Magdalinos, THEOCHEM, 1996,368,l. E. Fluck, G. Heckmann, E. Gorbunowa, M. Westerhausen and F. Weller, J. Orgunomet. Chem., 1997,529,223.

2

Pentaco-ordinated and Hexaco-ordinated Compounds

BY C. D. HALL

1

Introduction

As the topic of organophosphorus chemistry in general and hypervalent phosphorus chemistry in particular matures, so researchers in the field are able to provide substantial compilations of current knowledge in the area. Mironov et al. have summarised the reactions of five-coordinate phosphorus compounds containing P-H, P-N, and P-X (X=halogen) bonds with carbonyl compounds, imines and alkenes to afford new five- and six-coordinate phosphorus compounds. Incidentally, a review of the coordination chemistry of hydridophosphoranes2, although included last year, is worth another mention in this context as a topic of growing importance. Hexaco-ordinate phosphorus anions (e.g. PF6-) are common enough but it has only recently been realised that neutral compounds may also contain hexaco-ordinate phosphorus. A timely and comprehensive review of this to complement the extensive information comparing hypervalent phosphorus and silicon species3b is cited again in this year’s review despite its inclusion in Vol. 28. The novel cyclic phosphonite 1 has been used to prepare two cyclic tetraoxyphosphoranes (2,3)by oxidative addition.4a Pentaoxyphosphoranes (46) were also prepared by reaction of the appropriate phosphite with diol (7a or 7b). X-ray crystallography revealed hexacoordinate structures for 2 and 6 but 3-5 have pentacoordinate, tbp geometries. The eight-membered ring occupies the equatorial position in compounds 3 and 4 and the ring adopts an anti-chair conformation which precludes interaction of the sulfonyl oxygen atom with phosphorus. It is interesting to note that such a conformation places the phenyl group of 3 in a unique axial position. In the tbp of 5, the eight-membered ring occupies axial-equatorial sites in a syn twist-boat conformation. By contrast, in the highly fluorinated analogue 6a, oxygen donation from the sulfonyl group resulted in displacement from a square pyramid to 82.2% octahedral character compared to 27.9060 octahedral character in 2; These two phosphoranes provide the longest (2.646A for 2) and shortest (1.936A for 6) P-0 bond distances from a sulfone group. Reaction of 5 with catechols at 90°C is considerably faster than the analogous reaction with 4 but replacement of the sulfonyl group of 5 by sulfur gives a hexaco-ordinate structure (8) which is even more reactive towards catechols.4b Organophosphorus Chemistry, Volume 29 0The Royal Society of Chemistry, 1999

68

69

2: Pentuco-ordinutedand Hexuco-orciinuted Compounds

5

6a, Ar = c6F5 b. Ar = Ph

7a. R = But b, R = M e

Finally in this section, it will come as no surprise to learn that pentacoordinate structures continue to feature as intermediates in the solvolysis of phosphonium salts, specifically a series of alkylphenyl thiophenoxyphosphonium chloride~.~

70


2

Acyclic and Monocyclic Phosphoranes

Phosphorus pentachloride reacted with anthrone 9d9b at room temperature to give tetrachlorophosphorane 10) which decomposed on heating with more PC15 to form 9,l O-dichloroanthracene (12) presumably via 1 1.6 The analogous reaction of PC15 with 1-hydroxyanthrone (13) was considerably more complicated, however, and proceeded via (14) to give (15). 0

CI

OH

1

9a

pc15

&

CI 12

9b

1

heat, PC15

-POCIS

10 Zi3’P,-6O

&

11

-& CI

PC15

__t

P(O)CI2

15

\

13

-PC13, HCI

L

14

Phosphites (e.g. 16a and 16b) react with the perfluorinated diketones 17a and 17b to form a series of pentaoxyphosphoranes (18-21). Compound 20 crystallised in two similar conformations and single crystal X-ray structures of both molecules showed trigonal bipyramidal geometry about phosphorus with slightly different degrees of distortion towards the rectangular pyramid c~nfiguration.~ Likewise, phosphoramidites 22a,b reacted with 23 to form bicyclic phosphoranes 24a,b but 22c,d, with one or three phenyl groups attached to the ring, failed to react.

lSa, R = Et b. R = Ph

17a, RF = CF(CF& b, RF = (CF2)2CF3

18 19 20 21

R = Et, RF = CF(CF3)2 R = Et, RF = (CF2)2CF3 R = Ph, RF = CF(CF3)2 R = Ph, RF = (CF2)2CF3

71

2: Pen taco-orciinated and Hexuco-ordinated Compounds

/R P - N m C ,

R'-N

CF&OCOC2F5

23

0'N\R3

22a, R1,R2,R3= Me; R = CH2CH2CI

R'

b, R',R2,R3=Me; R = H c, R',R2 = Me; R3 = Ph; R = CH2CH2CI d, R',R2,R3 = Phi R = CH2CH2CI

24

Ester exchange of the oxyphosphorane 25 with ribonucleosides 26a-d gave a series of interesting, but labile, spirophosphoranes (27 a-d) which were characterised by MS and 'H/31P nmr in solution. Hydrolysis of 27a, followed by acetylation gave 28 with a high degree of regioselectivity.*

Base

Ph

pyridine

+

[email protected] 0-PI

I OMe OMe 25

27a

A& 0

Ho\

Me0-k.'

Ph

HO%Base OH

Ph

26a, Base= U

b, Base=A c, Base=G d, Base=C

27a-d

i, H20 ii, Ac20, pyridine

oH

28

The trihalophosphorane 29 reacted with epichlorohydrin (30) at - 70 "C in a highly regioselective fashion to give 95% of a 1:l addition product 31 which decomposed on heating to 32.' Various analogous reactions with 33 and 34 are also discussed within the same paper. 3

Bicyclic and Tricyclic Phosphoranes

The section begins with reports of two mechanistic studies relevant first to phosphate ester hydrolysis and secondly to an olefin-forming reaction akin to the Homer-Wadsworth-Emmons reaction but involving a spirooxyphosphoranyl

72


29

31

aoj?n ' '

0

1

30

0

a o \ P B o/r p

'

33

heat

a o ; P 0
12 gave 102 possibly via 100.

'

Reaction of the tetra-t-butyl calixarene 103 with PCI5 gave rise to an unusual calixarene 104 containing 4-, 5- and 6-coordinate phosphorus. The isolated molecule, which was characterised by 3'P nmr and X-ray crystallography, adopted a non-standard geometry between partial cone and 1,2-alternate conformations.2' But

+ 3PC15

OH 103

But

-4HCI

OH

PC16 I

CI 104

4 Hexaco-ordinate Phosphorus Compounds The synthesis and remarkable resolution of a conJigurationaffystable tris(tetrachlorobenzene diolato) phosphate ion (105) has been achieved. The electron withdrawing effect of the twelve chlorine atoms in the three benzene rings apparently stabilises the molecule so that solutions of 105 at room temperature


80

7 CI

108

+

PAQ 106

107

11la,b

showed no variation of the specific rotation ([a3D2O = - 375) with time. The near perfect octahedral structure and absolute phosphorus configuration (P) of 105 (crystallised from EtOAc) were confirmed by X-ray crystallography.26 Oxidative addition of tetrachloro-o-benzoquinone(59) or phenanthraquinone (106) to 107 gave 108 and 109 respectively. Chlorine was also displaced from phosphorus by p-toluidine and dimethylamine to give another four compounds (1 10a,b and 11 la,b) with similar structures. X-ray crystallographic studies of 108, 109, llOa and l l l a revealed hexacoordination by virtue of donor action by sulfur as part of an eight-membered ring. Within this series, the geometries were displaced along a coordinate from sqp towards octahedral at levels ranging ftom 24% .to 7 1YO. The respective P-S distance decreased along the series from 3.04A to 2.48A as the octahedral character increased. The changes in 31Pchemical shift throughout the series correlated with the extent of octahedral character and analysis of the data provided an estimate of the lower limit to the electrophilicity of phosphorus that will induce formation of hexaco-ordinate geometry.27 Finally, to end at what is essentially the beginning (at least of this chapter!)

81

2: Pen taco-ordinuted and Hexaco-ordinateil Compounds

Cavell el al. have synthesised and characterised a series of neutral, hexacoordinate phosphorus compounds containing divalent, tridentate diphenol imine, azo and thio ligands.28 For example, the reaction of silylated Schiff base ligands (e.g. 112) with PCI5 gave the neutral, hexacoordinate compound 113 by elimination of two equivalents of Me3SiC1. Structures of this type were characterised by MS, multinuclear (including solid state) nmr and X-ray crystallography. Compound 113 crystallised with three independent molecules and half a molecule of acetonitrile per unit cell. The geometry was octahedral, all the cis0-P-Cl angles were within 2" of the idealised 90" geometry and the largest deviation from 90 " was the C1( 13)-P( 1)-N(1) angle at 95.4 ". The thio(bispheno1) derivative 114 was also prepared and its X-ray crystal structure again showed a strongly bonded six-coordinate phosphorus compound but in this case, in contrast to the imine (and analogous azo) structure, the molecule adopted afac coordination rather thap a rneriodinal disposition of the 0-N ligands. The P-S bond distance (at 2.33 1A) is the shortest yet observed for y-S internal coordination and approaches the $ngle bond distance29 of ca. 2.1A and the sum of the single covalent radii (2.14A) for phosphorus and sulfur.

N

PC15

112

113

'-

114

References 1

2

3 4

V. F. Mironov, R. A. Cherkasov and 1. V. Konovalova, Russ. J. Gen. Chem., 1996, 66 (3), 409. K. N. Gavrilov and I. S. Mikhel', Russ. Chew. Rev., 1996,65 (3), 225. (a) C. Y. Wong, D. K. Kennepohl and R. G. Cavell, Chem. Rev., 1996, 96, 1917; (b) R. R. Holmes, G e m . Rev., 1996,%, 927. (a) A. Chandrasekaran, R. 0. Day and R. R. Holmes, Inorg. Chem., 1997,36,2578;

82

5 6 7 8 9 10

11 12

13 14 15

16 17 18 19 20 21 22 23 24 25 26 27 28 29

Orgunophospllorus Chemistry

(b) R. R. Holmes, A. Chandrasekaran and R. 0. Day, Phosphorus, Sulfur unci Silicon, Relut. Chem., 1997, 120-121,43 I . G. Aksnes, Phosphorus, Sulfur und Silicon, Relut. Chem., 1996, 115,43. A. A. Kutyrev, S. J. Fomin, and V. V. Moskva, Russ. J. Gen. Chem., 1996, 66 ( S ) , 757. A. Kadyrov, I. Neda, T. Kaukorat, R. Sonnenburg, A. Fischer, P. G . Jones and R . Schmutzler, Chem. Ber., 1996, 129, 725. X. Chen, N.-J. Zhang, Y. Ma, and Y.-F. Zhao, Phosphorus, Sulfur unci Silicon, Relut. Chem., 1996, 118,257. V. F. Mironov, 1. V. Konovalova, and M.G . Khanipova, Russ. J. Gen. Chem., 1996, 66 (I), 66. A. E. Wroblewski and J. G. Verkade, J. Am. Chem. Soc., 1996,118, 10168. M. L. Bojin, S. Barkallah, and S. A. Evans Jr., J. Am. Chem. Soc., 1996,118, 1549. V. I. Namestnikov, Yu. G. Trishin, and V. K. Bel’skii, Russ. J. Gcw. Chem., 1996,66 (8), 1367. M. A. Pudovik, S. A. Terent’eva, and A. N. Pudovic, Russ. J. Gen. Chem., 1996, 66 (3), 355. L. I. Nesterova, D. M. Malenko, V. V. Pirozhenko, and A. D. Sinitsa, Russ. J. Gen. Chem., l997,67 ( I ) , 151. (a) S. Narasimhamurthy, N. Thirupathi, R . Murugavel and S. S . Krishnamurthy, Phosphorus, Sulfur and Silicon, Relut. Chem., 1994, 93-94, 221; (b) N. Thirupathi, S. S. Krishnamurthy, and J. Chandrasekhar, J. Chem. Soc., Chem. Commun., 1996, 1703. J. Krill, I. V. Shevchenko, A. Fischer, P. G. Jones and R. Schmutzler, Chem. Ber. Receuil, 1997, 130, 1479. I. Neda, V. A. Pinchuk, A. Thonnessen, L. Ernst, P. G. Jones, and R. Schmutzler, 2. Anorg. Allg. Chem., 1997,623, 1325. S. Volbrecht, A. Vollbrecht, J. Jeske, P. G. Jones, R. Schmutzler and W.-W. du Mont, Chem. Ber. Recuiel, 1997, 130, 819. I. Neda, C. Muller and R. Schmutzler, J. Fluorine Chem., 1997,86, 109. V. G. Ratner, E. Lork, K. I. Pashkevich, and G.-V.Roschenthaler, J. Fluorine Chem., 1997,85, 129. B. N. Anand and R. Bains, Indiun J. Chem., 1997,36A, 77. B. A. D’Sa and J. G. Verkade, J. Am. Chem. Soc., 1996,118, 12832. S. Arumugam and J. G. Verkade, J. Org. Chem., 1997,62,4827. I. Gardinier, B. F. Chuburu, A. Roignant, J. J. Yaouanc and H. Handel, J. Chem. Soc., Chem. Commun., 1996,2157. H. Thonnessen, P. G. Jones, R. Schmutzler and J. Gloede, Acru Crystullogr.. Smt. C., 1997, C53, 1310. J. Lacour, C. Ginglinger, C. Grivet and G. Bernardinelli, Angew. Chem., Int. Ed. Engl., 1997,36 (6), 608. D. J. Sherlock, A. Chandrasekaran, R. 0. Day, and R. R. Holmes, J. Am. Chem. Soc., 1997, 119, 1317. C. Y. Wong, R. McDonald, and R. Cavell, Inorg. Chem., 1996,35,325. L. Pauling, ‘The Nature of the Chemical Bond’, 3rd Ed., Cornell, Ithaca, NY, 1960.

3

Tervalent Phosphorus Acid Derivatives BY 0.DAHL

1

Introduction

A review on the reaction of quinones with phosphorus-containing reagents, including phosphites, phosphinites, and phosphonites, has appeared. Another review has been published on the synthesis and reactivity of tervalent fluoroalkoxy derivatives of phosphorus.2

'

2

Nucleophilic Reactions

2.1 Attack on Saturated Carbon. - The synthesis of 2-chloroethylphosphonic acid (1) has been o p t i m i ~ e d .The ~ best yield and purity was obtained by heating triisopropyl phosphite with an excess of I -bromo-2-chloroethane, followed by acid hydrolysis. Diethyl 3-bromopropylphosphonate (2) was prepared in 76% yield by the addition of one mol of triethyl phosphite to three mol of boiling 1,3-dibromopropane, thus largely avoiding the competing Arbuzov reaction with the bromoethane liberated during the r e a ~ t i o n .A ~ precursor (3) of a phosphinic acid transition state analogue has been prepared by opening of a p-lactone with dimethyl phenylph~sphonite.~ The easily generated lithiated diaminophosphine borane complex 4 can be alkylated, and even arylated, to give a range of aminophosphine borane complexes (5) useful for syntheses of dichlorophosphines.6 Some a-haloketones have been protected as the silyl enol ethers 6 and then gave the normal Arbuzov products with triethyl p h ~ s p h i t e . ~ 2.2 Attack on Unsaturated Carbon. - The kinetics and mechanism of the reaction of trimethyl phosphite with substituted benzylideneacetophenones have been studied.' The proposed mechanism change from rate-limiting attack on the carbonyl carbon to attack on the carbon atom p to the carbonyl group when the benzene rings are substituted with electron-withdrawing substituents (Scheme I). Cyclic enones, e.g. 7, react sluggishly with silyl phosphites and give mixtures of 1,2- and 1,6adducts. A catalytic amount of trimethylsilyl triflate has now been found to give 1,6adducts, e.g. 8, regioselectively and in high yields at O"C.9 Trialkyl phosphites with o-phthalaldehyde and Lewis acid catalysts gave labile I dialkoxyphosphorylisobenzofurans 9 which could be trapped with dienophiles. l o

Organophosphorus Chemistry, Volume 29 0The Royal Society of Chemistry, 1999 83

84


'Cl

Li

4

R 5 R = primhec. alkyl or aryl

(Et0)3P + X x C 0 2 R 6

An efficient route to enantiopure piperidin-2-ylphosphonic acid (10) has been published. It involves a tin tetrachloride catalysed addition of trimethyl phosphite to the oxazolopiperidine 11 to give 12, which could be separated in pure diastereomers.

''

Y

+ (Me0)3P

ki +

L

kl

(Me0)3P+

Scheme 1

3

OMe

Electrophilic Reactions

3.1 Preparation. - the first aminobis(dialky1amino)phosphines (13) have been prepared and characterised.'* They can be stored for weeks at low temperatures, but oligomerise slowly at room temperature in solution to 14. Some I-methoxy(15) and 1-dialkylaminophosphirenes(16) have been prepared from the corresponding 1-chlorophosphirenes. l 3 The first examples of bicyclophosphites

85

3: Tervulent Phosphorus Acid Derivutives

+ (R0)2P-OSiMe3

-

OSiMe3

TMSOTf

7

8

+ (R0)sP

CHO

BFrE120

Lil

@O

Diels-alder adduct

9 Ph.

1-

'n

11

10

12

derived from alkane-l,2,3-triols, 17 and 18, were obtained from the alcohol and tris(dimethy1amino)phosphine.l4 (RzN)2PCI + LiNH2

-35 "C

(R~N)zP-NH~

13 R = Pr', Cy or Ph

I OMe 15 R = But or Ph OTr

OH + (MeN)3P OH OTr

-

14 n = 3 and 4 mainly

I NR2 10 R = Et, Pr' or Tms

TrO 17

18 R = Et, Ph or

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