Metal Carbenes in Organic Synthesis

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Florencio Zaragoza Dorwald

Metal Carbenes in Organic Synthesis

@ W ILEY-VCH Weinheim - New York Chichester Brisbane - Singapore Toronto

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@ WILEY-VCH




@ W ILEY-VCH Weinheim - New York Chichester Brisbane - Singapore Toronto

Dr. Florencio Zaragoza Dorwald Novo Nordisk A/S MedChem Research Novo Nordisk Park DK-2760 Mbl0v - Denmark

This book was carefully produced. Nevertheless, author, editors and publisher do not warrant the information contained therein to be free of errors. Readers are adviced to keep in mind that statements, data, illustrations, procedural details or other items may inadvertently be inaccurate.

Library of Congress Card No. applied for.

A catalogue record for this book is available from the British Library.

Deutsche Bibliothek Cataloguing-in-Publication Data: Zaragoza Dorwald, Florencio: Metal carbenes in organic synthesis / Florencio Zaragoza Dorwald. Weinheim ; New York ; Chichester ; Brisbane ; Singapore ; Toronto : Wiley-VCH, 1999 ISBN 3-527-29625-5

OWILEY-VCH Verlag GmbH, D-69469 Weinheim (Federal Republic of Germany). 1999 Printed on acid-free and chlorine-free paper. All rights reserved (including those of translation into other languages). No part of this book may be reproduced in any form - by photoprinting, microfilm, or any other means nor transmitted or translated into a machine language without written permission from the publishers. Registered names, trademarks, etc. used in this book, even when not specifically marked as such, are not to be considered unprotected by law. Composition: Fa. Richarz Publikations-Service GmbH., D-53734 Sankt Augustin. Printing: betz-druck GmbH, D-64291 Damstadt Bookbinding: J. Schaffer GmbH & Co. KG., D-67269 Grunstadt Printed in the Federal Republic of Germany.

Foreword

In the period between the discovery in the late 1950s that copper catalyzed the addition of diazo compounds to olefins to yield cyclopropanes and the recent introduction of olefin metathesis into the synthesis of fine chemicals, a wide variety of useful organic transformations that involve metal carbene intermediates has been discovered. Since most of the reactions of metal carbenes result in the formation of carbon-carbon bonds, the reactions have played a major role in the organometallic revolution in organic synthetic technology during the past few years. Zaragoza-Dorwald has assembled this large array of reactions into a system that allows the common feature of the reactions to be recognized. After outlining the bonding description of the types of complexes, he uses the simple structure types to divide an amazing array of reactions that range from cyclopropanation to the olefination of carbonyls into groups that follow a general mechanistic pathway. The book follows a consistent outline that efficiently provides the active chemist with the information needed to follow up a reaction type. Each section starts with a definition of the metal carbene structure along with a general mechanistic scheme for the preferred reactions of that type of carbene. A few specific examples are discussed to demonstrate the key features, and then a large number of examples are tabulated. At the end of each section an experimental procedure is presented that provides the details of a representative reaction. I found the progression from general to specific examples an extremely efficient presentation of important ideas without excessive details. For example, his treatment of the Dotz and related reactions allowed him to introduce many of the subtle features of this complex reaction in a concise fashion. This approach also allows the book to be read at many levels. The brief introduction and the array of tables allow for a rapid overview of the field, while the extensive references and experimental procedures provide ample detail for an in-depth study of specific reactions. Along a number of reviews have been written on specific aspects of metal carbene complex chemistry, this book describes in one place the array of reactions involving these intermediates and provides the structural basis that ties them together. Although some parts of the book might quickly become out of date, this concise presentation of all the aspects of the use of carbene complexes in synthesis will help provide the impetus for even more rapid developments in this field of research. Pasadena, October 1998

Robert H. Grubbs (California Institute of Technology, Pasadena)


Preface

To the memory q f m yfriend and colleague Lutz Richter

In recent decades there has been an exponential increase in the use of transition metals in organic synthesis. Among the different types of transition-metal-based reagent described, carbene complexes are among the most versatile. The applications of carbene complexes include both their use as catalysts for a number of important synthetic transformations and their utilization as stoichiometric reagents. The aim of this book is to give the reader a well-structured overview of the most important applications of carbene complexes in organic synthesis. Special emphasis has been given to recent innovations, in an attempt to pinpoint new and promising research areas. Hopefully this will give plenty of inspiration for the development of new research projects. As an organic chemist I consider reaction mechanisms of crucial importance, both for the classification of reactions and for synthesis-planning. For this reason mechanisms are proposed for almost all the reactions described herein. Most of these mechanisms have not yet been rigorously proven, however, and should be considered as preliminary. The subject of this book has been organized in three main sections: preparation and applications of heteroatom-substituted carbene complexes (Fischer-type carbenes), non-heteroatom-substituted carbene complexes, and acceptor-substituted carbene complexes. In each section the different types of reaction have been ordered either according to the mechanism or according to the type of product. In addition to a selection of illustrative examples, several experimental procedures have been included. These were chosen taking into account safety, availability of starting materials, relevance of the products, and general interest. I would like to thank my colleagues and supervisors at Novo Nordisk A/S, in particular Jesper Lau and Behrend F. Lundt, for their support and encouragement. It is also a pleasure to acknowledge Kilian W. Conde-Friboes, Robert Madsen, and Thomas Redemann for proofreading various sections of the manuscript and for their helpful comments and suggestions.


Table of Contents

Abbreviations . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .

XI11

Experimental Procedures . . . . . . . . . . . . . . . . . . . . . . . . .

XV

1 1 .1 1.2

1.3 1.4

2 2.1 2.1.1 2.1.1.1 2.1.1.2 2.1.1.3 2.1.2 2.1.3 2.1.4 2.1.5 2.1.5.1 2.1.5.2 2.1.6 2.1.7 2.1.8 2.1.9 2.2 2.2.1 2.2.2 2.2.3 2.2.4 2.2.5

. . . . . . . . . . . . . . . . Reactivity of Carbene Complexes . . . . . . . . . . . . . . . . .

1

Fischer-Type and Schrock-Type Carbene Complexes: Theoretical Treatment . . . . . . . . . . . . . . . . . . . . . . . . . . . . . Olefin Metathesis and Olefin Cyclopropanation . . . . . . . . . . Characteristic NMR Data . . . . . . . . . . . . . . . . . . . . .

3 5 9

Heteroatom-Substituted Carbene Complexes . . . . . . . . . . Generation of Heteroatom-Substituted Carbene Complexes . . . . From Acyl Complexes . . . . . . . . . . . . . . . . . . . . . . From Acyl Complexes Generated from Carbonyl Complexes . . . From Acyl Complexes Generated from Metallates . . . . . . . . From Acyl Complexes Generated by Other Methods . . . . . . . From Isonitrile Complexes . . . . . . . . . . . . . . . . . . . . From a-Haloiminium Salts and Metallates . . . . . . . . . . . . From Carboxamides and Metallates . . . . . . . . . . . . . . . . From Vinylidene Complexes . . . . . . . . . . . . . . . . . . . From Vinylidene Complexes Generated from Alkynes . . . . . . From Vinylidene Complexes Generated from Alkynyl Complexes From Carbenes and Carbenoids . . . . . . . . . . . . . . . . . . From Alkyl Complexes by a-Abstraction . . . . . . . . . . . . . From Carbyne Complexes . . . . . . . . . . . . . . . . . . . . . Other Methods . . . . . . . . . . . . . . . . . . . . . . . . . .

13 14 14 15 18 19 20 20 21 25 25 25 27 29 32 33

Synthetic Applications of Heteroatom-Substituted Carbene Complexes . . . . . . . . . . . . . . . . . . . . . . . . . . . . General Considerations . . . . . . . . . . . . . . . . . . . . . . Demetallation and Formation of Acyclic Products . . . . . . . . . Photochemical Transformations . . . . . . . . . . . . . . . . . . Cyclopropanation . . . . . . . . . . . . . . . . . . . . . . . . . Thermal Benzannulations . . . . . . . . . . . . . . . . . . . . .

34 35 37 41 45 49

The Carbon-Metal Double Bond

1

X

Table o j Contents

2.2.5. I 2.2.5.2 2.2.6 2.2.6.1 2.2.6.2 2.2.6.3 2.2.6.4 2.2.7 2.2.8

The Dotz Benzannulation Reaction . . . . . . . . . . . . . . . . 49 Other Thermal Benzannulations . . . . . . . . . . . . . . . . . . 5.5 Formation of Five-Membered Rings . . . . . . . . . . . . . . . . 56 Cyclization of (1,3.Butadien. 1.yl)carbene Complexes . . . . . . . 56 Cyclization of Functionalized Carbene Complexes . . . . . . . . 63 Rearrangement of Ammonium Ylides . . . . . . . . . . . . . . . 64 Other Methods . . . . . . . . . . . . . . . . . . . . . . . . . . 65 Formation of Six.Membered. Non-Aromatic Carbocycles and Six-Membered Heterocycles . . . . . . . . . . . . . . . . . . . . 66 Formation of Seven-Membered Rings . . . . . . . . . . . . . . . 70

3

Non-Heteroatom-Substituted Carbene Complexes

3.1 3.1.1 3.1.2 3.1.2.1 3.1.2.2 3.1.2.3 3.1.2.4 3.1.3 3.1.3.1 3. I .3.2 3.1.4 3.1.4.1 3.1.4.2 3.1.5 3.1.6 3.1.7 3.1.8

Generation of Non-Heteroatom-Substituted Carbene Complexes . a-Abstraction of Electrophiles (Nucleophilic Abstraction) . . . . . a-Abstraction of Nucleophiles (Electrophilic Abstraction) . . . . . a-Abstraction of Hydride . . . . . . . . . . . . . . . . . . . . . a-Abstraction of Oxygen-Bound Leaving Groups . . . . . . . . . a-Abstraction of Thioethers . . . . . . . . . . . . . . . . . . . . a-Abstraction of Halides . . . . . . . . . . . . . . . . . . . . . From Ylides . . . . . . . . . . . . . . . . . . . . . . . . . . . . From Diazoalkanes . . . . . . . . . . . . . . . . . . . . . . . . From Other Ylides . . . . . . . . . . . . . . . . . . . . . . . . From Carbyne Complexes . . . . . . . . . . . . . . . . . . . . . Nucleophilic Additions to Carbyne Complexes . . . . . . . . . . Electrophilic Additions to Carbyne Complexes . . . . . . . . . . From Alkynyl and Alkenyl Complexes . . . . . . . . . . . . . . From Alkyne and Cyclopropene Complexes . . . . . . . . . . . . By [2 + 21 Cycloreversion . . . . . . . . . . . . . . . . . . . . Other Methods . . . . . . . . . . . . . . . . . . . . . . . . . .

76 78 82 83 84 87 89 90 90 93 93 94 96 98 98 00 101

3.2

Synthetic Applications of Non-Heteroatom-Substituted Carbene Complexes . . . . . . . . . . . . . . . . . . . . . . . . . . . . General Considerations . . . . . . . . . . . . . . . . . . . . . . Cyclopropanation . . . . . . . . . . . . . . . . . . . . . . . . . Stoichiometric Cyclopropanations . . . . . . . . . . . . . . . . . Catalytic Cyclopropanations with Diazoalkanes . . . . . . . . . . Catalytic Cyclopropanations with Other Carbene Precursors . . . C-H Insertions . . . . . . . . . . . . . . . . . . . . . . . . . . C-H Insertions of Nucleophilic Carbene Complexes . . . . . . . C-H Insertions of Electrophilic Carbene Complexes . . . . . . . Carbonyl Olefination . . . . . . . . . . . . . . . . . . . . . . . Carbonyl Methylenation . . . . . . . . . . . . . . . . . . . . . . Carbonyl Olefination with Higher Alkylidenes . . . . . . . . . . Olefin Metathesis . . . . . . . . . . . . . . . . . . . . . . . . . General Considerations . . . . . . . . . . . . . . . . . . . . . . Heterogeneous Catalysts . . . . . . . . . . . . . . . . . . . . . .

103 103 10.5 106 114 116 119 119 122 125 125 129 134 135 138

3.2.1 3.2.2 3.2.2.1 3.2.2.2 3.2.2.3 3.2.3 3.2.3.1 3.2.3.2 3.2.4 3.2.4.1 3.2.4.2 3.2.5 3.2.5.1 3.2.5.2

.......

75

XI

Tuble of Contents

3.2.5.3 Homogeneous Catalysts . . . . . . . . . . . . . . . . . . . . . . 140 3.2.5.4 Scope and Limitations of Molybdenum- and Ruthenium-Based Homogeneous Catalysts . . . . . . . . . . . . . . . . . . . . . . 143 3.2.5.5 Ring-Opening Metathesis Polymerization (ROMP) . . . . . . . . 144 3.2.5.6 Ring-Closing Metathesis (RCM) . . . . . . . . . . . . . . . . . 148 3.2.5.7 Cross Metathesis . . . . . . . . . . . . . . . . . . . . . . . . . 161 3.2.5.8 Ring-Opening Cross Metathesis . . . . . . . . . . . . . . . . . . 168 Other Applications of Non-Heteroatom-Substituted Carbene 3.2.6 Complexes . . . . . . . . . . . . . . . . . . . . . . . . . . . . 169

. . . . . . . . . . . 171

4

Acceptor-Substituted Carbene Complexes

4.1 4.1.1 4.1.1.1 4 .1. 1.2 4.1.2 4.1.3

Generation of Acceptor-Substituted Carbene Complexes . . . . . From Acceptor-Substituted Diazomethanes . . . . . . . . . . . . Preparation of Acceptor-Substituted Diazomethanes . . . . . . . . Catalysts for Diazodecomposition . . . . . . . . . . . . . . . . . From Other Ylides . . . . . . . . . . . . . . . . . . . . . . . . From Other Carbene Complexes . . . . . . . . . . . . . . . . .

171 172 172 175 176 176

4.2

Synthetic Applications of Acceptor-Substituted Carbene Complexes . . . . . . . . . . . . . . . . . . . . . . . . . . . . General Considerations . . . . . . . . . . . . . . . . . . . . . . C-H Insertions . . . . . . . . . . . . . . . . . . . . . . . . . . Scope and Limitations . . . . . . . . . . . . . . . . . . . . . . . Stereoselectivity . . . . . . . . . . . . . . . . . . . . . . . . . . Intramolecular 1,2.CH . Insertions . . . . . . . . . . . . . . . . Intramolecular 1,3. CH . Insertions . . . . . . . . . . . . . . . . Intramolecular 1,4. CH . Insertions . . . . . . . . . . . . . . . . Intramolecular 1 ,5. CH . Insertions . . . . . . . . . . . . . . . . Intramolecular 1,6. and 1,7. C-H Insertions . . . . . . . . . . . Intermolecular C-H Insertions . . . . . . . . . . . . . . . . . . Si-H Insertions . . . . . . . . . . . . . . . . . . . . . . . . . . C-C Insertions . . . . . . . . . . . . . . . . . . . . . . . . . . X-H Insertions (X: N. 0. S) . . . . . . . . . . . . . . . . . . N-H Insertions . . . . . . . . . . . . . . . . . . . . . . . . . . O-H Insertions . . . . . . . . . . . . . . . . . . . . . . . . . . S-H Insertions . . . . . . . . . . . . . . . . . . . . . . . . . . Y lide Formation . . . . . . . . . . . . . . . . . . . . . . . . . . Ammonium Ylides . . . . . . . . . . . . . . . . . . . . . . . . Azomethine Ylides . . . . . . . . . . . . . . . . . . . . . . . . Nitrile Ylides . . . . . . . . . . . . . . . . . . . . . . . . . . . Oxonium Ylides . . . . . . . . . . . . . . . . . . . . . . . . . . Carbonyl Y lides . . . . . . . . . . . . . . . . . . . . . . . . . . Sulfonium Ylides . . . . . . . . . . . . . . . . . . . . . . . . . Thiocarbonyl Ylides . . . . . . . . . . . . . . . . . . . . . . . . Other Ylides . . . . . . . . . . . . . . . . . . . . . . . . . . . Cyclopropanation . . . . . . . . . . . . . . . . . . . . . . . . .

178 178 179 179 180 180 181 181 182 189 189 192 193 193 194 196 197 198 198 202 203 205 206 213 216 217 218

4.2.1 4.2.2 4.2.2.1 4.2.2.2 4.2.2.3 4.2.2.4 4.2.2.5 4.2.2.6 4.2.2.7 4.2.2.8 4.2.3 4.2.4 4.2.5 4.2.5.1 4.2.5.2 4.2.5.3 4.2.6 4.2.6.1 4.2.6.2 4.2.6.3 4.2.6.4 4.2.6.5 4.2.6.6 4.2.6.7 4.2.6.8 4.2.7

. . . . . . .

XI1

Table of Contents

4.2.7.1 4.2.7.2 4.2.7.3 4.2.7.4 4.2.8

Scope and Limitations . . . . . . . . . . . . . . . . . . . . . . . 218 219 Stereoselectivity . . . . . . . . . . . . . . . . . . . . . . . . . . Intramolecular Cyclopropanations . . . . . . . . . . . . . . . . . 220 Intermolecular Cyclopropanations . . . . . . . . . . . . . . . . . 224 Formal 1,3-Dipolar Cycloadditions of Acyl- and Vinylcarbene Complexes . . . . . . . . . . . . . . . . . . . . . . . . . . . . 226 Ring Fission of Pyrroles and Furans . . . . . . . . . . . . . . . 231 Other Synthetic Applications of Acceptor-Substituted Carbene Complexes . . . . . . . . . . . . . . . . . . . . . . . . . . . . 232

4.2.9 4.2.10 5

Bibliography . . . . . . . . . . . . . . . . . . . . . . . . . . .

233

Index

...................................

267

Abbreviations

acetyl acetylacetonato acyclic diene metathesis ally1 2,6-di(tert-butyl)-4-methylphenol benzyl tert-butyloxycarbon y 1 boiling point butyl ceric ammonium nitrate, (NH4),Ce(N0,), caprolactam benzyloxycarbonyl 1,5-~yclooctadiene 1,3,5-cyclooctatriene $-cyclopentadienyl pentamethyl-qs-cyclopentdienyl cy clohex y 1 1,2-dichloroethane diastereomeric excess decomposition dimethyl acetylenedicarboxylate 1,2-dimethoxyethane N,N-dimethy lformamide 4-(dimethy1amino)pyridine dimethyl sulfoxide 1,2-bis(diphenylphosphino)ethane enantiomeric excess equivalents hexyl hexafluoroacetylacetonato hexamethylphosphoric triamide ligand metal M MCPBA 3-chloroperoxybenzoic acid methox ymethy 1 MOM

Ac acac ADMET All BHT Bn Boc bP Bu CAN Cap Cbz COD COT CP CP’ CY DCE de dec . DMAD DME DMF DMAP DMSO dPPe ee eq. Hex hfacac HMPA

XIV

Abbreviations

MS mP MTO mwt NP Ns Pht piv PMP PNB Pol Pr PYr RCM ROMP salen TBAF TBS TES Tf TFA THF THP TIPS TLC TMEDA TMS To1 TP’ Tr Ts

molecular sieves melting point methylrhenium trioxide, CH3Re03 molecular weight neopentyl, 2,2-dimethylpropyl (trimethylsily1)methyl phthaloy 1 pivalate, 2,2-dimethylpropionate 4-methoxyphenyl 4-nitrobenz y l polymeric support ProPYl p yridine ring-closing metathesis ring-opening metathesis polymerization bis(salicyla1dehyde)ethylenediimine tetrabutylammonium fluoride tert-buty ldimethylsily 1 trieth ylsil yl trifluoromethanesulfony1 trifluoroacetic acid tetrahydrofuran 2-tetrahy dropyrany l triisopropylsily 1 thin-layer chromatography N,N,N’,N’-tetramethylethy lenediamine trimeth ylsilyl 4-methylpheny l hydrotris( 3,5-dimethyl- 1-pyrazolyl)borato trityl p-toluenesulfonyl, tosyl

Experimental Procedures

Experimental Procedure 2.1.1. Preparation of a Chromium Carbene Complex from Chromium Hexacarbonyl: [Methoxy(methyl)carbene]pentacarbonylchromium

MeLi

Cr(CO),

OLi

[Me,O][EF,]

OMe

(CO),Cr 92%

15

Experimental Procedure 2.1.2. Preparation of a Chromium Carbene Complex from a Carboxamide: { [(4S)-2,2-Dimethyl-4-phenyloxazolidin-3-yl]me~ylene} pentacarbonylchromium 1. Na,[Cr(CO),] 2. Me,SiCI 3.AI,03

*

(c0)5cL

93% Ph

Ph

23

Experimental Procedure 2.1.3. Preparation of an Iron Carbene Complex by &Abstraction of Hydride: Dicarbonyl(~5-cyclopentadienyl)(phenylthiocarbene) iron hexafluorophosphate

1. NalHg 2. PhSCH,CI

[Cp(CO),Fe],

51%

OC SPh Cp-kd

I

oc

[Ph&l[pF~l

OC,

78%

29

XVI


Experimental Procedure 2 2-Benzyl-4-benzyloxy-4din-3-one

Photolysis of a 1-2,3,4,4a,7,7a-he

45 Experimental Procedure Complex: Diethyl trans-3OMe

(co)p=(

+

E

Ph

48

Experimental Procedure 2.2.4. Benzannulation with a Chromium Furylcarbene Complex: 5,6-Diethyl-4,7-dihydroben Cr(CO),

@OMe

+

54


XVII

Experimental Procedure 2.2.5. Cyclopentannulation with a Tungsten Alkynylcarbene Complex: 1-(1-Ethoxy-3-phenyl-5,9b-dihydro-4H-cyclopenta[u]naphthalen-9-y1)pyrrolidine

59

Experimental Procedure 2.2.6. Cyclopentannulation with a Molybdenum Arylcarbene Complex: 3-Hexyl-5-methyl- 1-indanone MOW),

1.9ooc 2. CAN +

Hex

61

Experimental Procedure 2.2.7. Diels-Alder Reaction of a Tungsten Vinylcarbene Complex: Methyl 2-(2-Furyl)-5-methyl-4-oxo-1-cyclohexanecarboxylate

70

XVIII

Experimentul Procedures

Experimental Procedure 2.2.8. [4 + 31 Cycloaddition of a Chromium Vinylcarbene Complex to a l-Azadiene: truns-4-(2-Furyl)-2-methoxy-5-methyl-4,5dihydro-3H-azepine

71

Experimental Procedure 2.2.9. [4 + 31 Cycloaddition of a Chromium Carbene Complex to a 2-Aminodiene: 6-(2-Furyl)bicyclo[5.4.0]undecan-2,4-dione

73

Experimental Procedure 3.1.1. Preparation of a Molybdenum Carbene Complex by Nucleophilic Abstraction: (2,6-Diisopropylphenylimido)bis[1,l-bis(trifluoromethyl)ethoxy](2-methyl-2-phenyl- 1-propylidene)molybdenum

(NH&MoA

four steps

4%

(FaC),MeC-O-?$oAph / (F,C),MeC-0

80


XIX

Experimental Procedure 3.1.2. Preparation of an Iron Vinylidene Complex by Electrophilic Abstraction: Carbonyl(~5-cyclopentadienyl)(dimethylvinylidene)(tripheny1phosphine)iron tetrafluoroborate HBF,, TfzO

Of?Fe-$/ Ph,P

86

Experimental Procedure 3.1.3. Preparation of a Ruthenium Carbene Complex from a Diazoalkane: Dichloro-bis(tricyclohexy1phosphine)benzylideneruthenium 1. PhCHN,, -78 OC, 5 min 2. PCy,, 20 O C , 30 min CH,CI, (PPh,),RuCI2

.c

pcY$ CI,

I

ph

-

/

91

Experimental Procedure 3.1.4. Preparation of a Molybdenum Vinylidene Complex from a Carbyne Complex: Tetrabutylammonium { Cyano(ethoxycarbony1) vinylidene} (dicarbonyl){ hydro-tris(3,5-dimethyl-1-pyrazolyl)borato} molybdenum [NEt,]ITp'Mo(CO),]

80%

co I Tp'-Mo+CI A 0

NC-C0,Et

100%

co

C02Eq-

Tp'-ho=C+

NBU,+

CN

60

95

Experimental Procedure 3.2.1. Cyclopropanation with an Iron Carbene Complex: 1,l-Diphenylcyclopropane 100 OC, dioxane 14h c

Ph

88%

x

Ph

Ph

106

xx


113

124

129

133

133


XXI

Experimental Procedure 3.2.7. RCM with a Tungsten Catalyst in Homogeneous Phase: Diethyl 3-Cyclopentene-1,l -dicarboxylate

* Et0,C

Et0,C

C0,Et

6

C0,Et

PbEt4,PhMe 91%

150

Experimental Procedure 3.2.8. RCM with a Ruthenium Catalyst in Homogeneous Phase: 2-Phenyl-3,6-dihydro-2H-pyran

-0

L

OPh +

. )

86%

156

Experimental Procedure 3.2.9. Cross Metathesis with a Molybdenum Catalyst in Homogeneous Phase: (E)- 1-Phenyl-1-octene 2,6-(iPr),C,H,,

N

“fc

(CF3),M*CO--EjlCi

Ph-

+

3

(CF,),MaCC)’

Ph

94%

161

XXII


Experimental Procedure 4.1.1. Preparation of an Enantio ically pUre Rhodium(I1) Complex: Dirhodium(I1) Tetrakis[methyl2-0~0-1-(3-phenylpropanoyl)4(S)-imidazolidinecarboxylate]; Rh2(4S-MPP1M),(MeCN),

175

Experimental Procedure 4.2.1. Prepara Insertion: Ethyl trans-2-0x0- 1,4-diph

01e~ularC-H

Rh,(OAch

C0,Et 6h

CHzC'z

61W

182 Experimental Procedure 4.2.2. Preparation of an Indole by Intramolecular C-H Insertion: Methyl (2S)-2-(3-Acetyl-2-hydroxy-S-nitro1H-I -indolyl)-3phenylpropanoate Ph

65%

187

Experiinetztul Procedures

XXIII

Experimental Procedure 4.2.3. Alkylation of Indole by Intermolecular C-H Insertion: 3-( lH-3-Indolyl)-2,4-pyrrolidinedione

0 1

+

I - ' 64%

#

192 Experimental Procedure 4.2.4. Etherification of a Serine Derivative by Intermolecular 0-H Insertion: Methyl (2S)-3-[(Ethoxycarbonyl)methoxy]-2-(benzyloxycarbony1amino)propanoate

197 Experimental Procedure 2.5. Ammonium YliL,: Formation and Stevens Rearrangement: Diethyl2-Benzyl-2- { [(ethoxycarbonyl)methyl](methyl)amino } malonate EtozC~cozEt NZ

+

Cu,PhMe PhnNnCO,Et

I

EtozC

CozEt

__c

92%

Ph3(NACOzEt

I

200 Experimental Procedure 4.2.6. Oxonium Ylide Formation and 2,3-Sigmatropic Rearrangement: Ethyl 2,5-Dimethoxy-4-pentenoate

205

XxTv


Experimental Procedure

d Intramolecular

e0 C0,Et

BF,OEt,

* 100%

0 C0,Et

92%

bMe

Me

210

Experimental Procedure 4.2.8. Enantioselective, Intramolecular Cyclopropanation: 6,6-Dimethyl-3-oxabicyclo[3.1 .O]hexan-2-one

84% 92% ee

22 1

Experimental Procedure 4.2.9. Enantioselective, Intermolecular Cyclopropanation: Ethyl (lS)-2,2-Dimethyl- 1-cyclopropanecarboxylate

A +

N2 NEf, 20 "C, THF, 3 h

9 N/NYRhc'(cp'' LN-Ph

lgam has cooled to room in dry, degassed room temperature

31

2. I Generation of Heteroatom-Sub.Ftituted Carbene Complexes

Table 2.9. Preparation of heteroatom-substituted carbene complexes by a-abstraction. Starting Material

1

COC\ PlFe--\ Ph,P

2

3

04

Yield

>80% [I781

1'

78%

[I791

81%

[I801

IPh,CI[PF,I

OC\ Cp-,FeT OC

BF,, 20 "C, C6H6

Ref.

1'

OC\ Cp-FeT PF,Ph,P OMe

S ' Ph

OC\ Cp- Fe-CF,

Product

[Ph3CI[PF61 OMe

OC\ Cp-Fe

Od

Reagents, Conditions

PF,-

SPh

OC, F1' Cp-Feq BF,Od F

for 3 h. The ferrate solution is decanted from the amalgam into a round-bottom flask, and freshly distilled chloromethyl phenyl sulfide (9.1 mL, 10.8g, 68.1 mmol) is added dropwise at 0 "C by means of a syringe over 10 min. The mixture is stirred at room temperature for 1 h and then concentrated to dryness under reduced pressure. Degassed dichloromethane (50 mL) and degassed hexane (100 mL) are added and the mixture is left to settle for 1 h. Filtration through neutral alumina (100 g), concentration, and column chromatography (silica gel, dichloromethanehexane 2: 1) yields 8.7 g (5 1%) Cp(CO),FeCH,SPh as bright yellow crystals, mp 66 "C. Triphenylmethyl hexafluorophosphate (1 1.3 g, 29.1 mmol) is added in one portion to a solution of Cp(CO),FeCH,SPh (8.7g, 29.0 mmol) in degassed dichloromethane (75 mL). The resulting dark green mixture is stirred for 5 min, and anhydrous diethyl ether (degassed) is added while stirring. Filtration, rapid washing with cold diethyl ether (3x 25 mL) and recrystallization from dichloromethane and diethyl ether gives 10.1 g (78%) of the title complex as golden-yellow crystals, mp 126 "C (dec.). The compound slowly abstracts hydride from diethyl ether, and is slightly air- and moisture-sensitive, but can be stored for a few months at 25 "C under nitrogen. 'H NMR (200 MHz, CD,Cl,) 6 5.64 (s, 5H), 7.62 (s, 5H), 15.52 (s, 1H). 13C NMR (75 MHz, CD,NO,) 6 90.40, 128.45, 131.52, 133.29, 142.31, 208.72, 317.35.

32

2 Heteroatom-Substituted Carbene Complexes

2.1.8 From Carbyne Complexes Similar to vinylidene complexes, carbyne complexes can also react with nucleophiles to yield heteroatom-substituted carbene complexes (Figure 2.14) [ 122,1811841, When imines are the nucleophiles used, the initially formed iminium intermediates can undergo intramolecular electrophilic alkylation of the other ligands (e.g. Entry 2, Table 2.10; see also [143]). In addition to this, carbyne complexes can also react with azides to give metallatriazoles [ 185,1861 (Entry 6, Table 2.10). Table 2.10. Heteroatom-substituted carbene complexes prepared from carbyne complexes. Starting Material


Product

NaOiPr

Yield

Ref.

69%

[187]

45%

[I881

63%

[189]

91%

[I901

bh

oc

Ph PheN, NEt3, 20 "C, CH,CI,, 1 h

oc

BudNCl, -50 "C, CH2C1,, 1 h

oc

4

oc

-20 "C, CH,CI,

oc

Cp-ReLToJ'BC1,\ I

>co

-20 "C, CHZCI,

oc

oc \

cp-wI

oc

N,-CO,Me 20 "C, pentane,

48 h

Cp-ke=(I

NF

OC

Cp T R e

oc

<Sc, oc

Meo2C7

\ /N--N

cp-w

Od

P

40%

[I901

85%

[I861

2. I Genercition of Heternatom-Substituted Curhene Complexes

33

Fig. 2.14. Conversion of electrophilic carbyne complexes into heteroatom-substituted carbene complexes.

2.1.9 Other Methods As will be discussed more thoroughly in Section 3.2.5, transition metal carbene complexes can mediate olefin metathesis. Because heteroatom-substituted carbene complexes are usually less reactive towards olefins than the corresponding nonheteroatom-substituted complexes, it is, e.g., possible to use enol ethers to terminate living polymerization or other types of metathesis reaction catalyzed by a nonheteroatom-substituted carbene complex. Olefin metathesis can also be used to prepare new heteroatom-substituted carbene complexes (Figure 2.15, Table 2.1 1).

X = OR, NR,

Fig. 2.15. Preparation of heteroatom-substituted carbene complexes by olefin metathesis.

Donor-substituted alkynes can insert into the C-M double bond of alkoxycarbene complexes, yielding donor-substituted vinylcarbene complexes [ 191,1921. In addition to this, photolysis or thermolysis of a-alkoxycyclopropyl carbonyl complexes or a-alkoxycyclobutanoyl complexes can lead to rearrangement to metallacyclic carbene complexes (Table 2.1 1). This methodology has not been used as extensively for the preparation of carbene complexes as the other methods described above. Photolysis of cationic alkoxycarbene iron complexes [ 1931 or alkoxycarbene manganese complexes [ 1941 has been used to replace carbonyl groups by other ligands. The alkylidene ligand can also be transferred from one complex to another by photolysis [ 1951. Transfer of alkylidene ligands occurs particularly easily from diaminocarbene complexes, and has become a powerful synthetic method for the preparation of imidazoline-2-ylidene complexes [ 155,1961. The reaction of alkoxy(ary1)carbene iron complexes with two equivalents of an isonitrile leads to the formation of azetidin-2-ylidene complexes [ 1971, For other reactions of Fischer-type carbene complexes with isonitriles see [ 1981.

34

2 Heteroatom-Substituted Curbene Complexes

Table 2.11. Preparation of heteroatom-substituted carbene complexes by photolysis and olefin metathesis. Starting Material


Product CP,

,co

R

o

hv, C,H,, CO

O

CP,

hv, C6D6

M

Yield

Ref.

30%

[199]

48%

[200]

e

co

&,Me

dYzCP 45%

hv, 20 "C, CbD6, 3d

[201]

H

(cisltrans 78:22)

iNpoMe Cr(CO),

O-l

75%

[202]

65%

[125]

PhKOMe I 10 "C, PhMe,

6h

Ph (CO),Cr=( Ph

0x0

20 "C, heptane

2.2 Synthetic Applications of Heteroatom-Substituted Carbene Complexes Heteroatom-substituted (Fischer-type) carbene complexes are mostly used as stoichiometric reagents. For this reason only carbene complexes of reasonably cheap metals, such as chromium, molybdenum, tungsten, or iron have found broad application in organic synthesis. Because many of the reactions involving heteroatom-substituted carbene complexes are cascade processes involving several different reaction types, they are

2.2 Synthetic Applicutions of Heteroatom-Substituted Curbene Complexes

35

difficult to organize according to reaction mechanism. In the following sections, therefore, the different synthetic applications of these complexes will be classified in terms of the type of product obtained. The focus will be on reactions which lead to metal-free products. Several reviews have appeared in which different aspects of the applications of heteroatom-substituted carbene complexes in organic synthesis are discussed [203 -2101.

2.2.1 General Considerations The heteroatom-substituted carbene complexes most frequently used in organic synthesis are carbonyl complexes of the type (CO),M=C(X)R (M: Cr, Mo, W; X: OR, NR,; R: H, alkyl, aryl, vinyl, alkynyl, etc.). To some extent such complexes behave as carboxylic esters or amides, the (CO),M=C group having electronic properties similar to those of a carbonyl group (Figure 2.16).

Fig. 2.16. Typical reactions of Fischer-type alkylcarbene complexes.

The carbene-bound alkyl groups are acidic { pK, [(CO),Cr=C(OMe)Me in H,O] 12.3) and can be easily deprotonated and alkylated [45,211,212] or acylated [213] (Figure 2.16). Stereoselective aldol-type additions can be realized with the aid of Fischer-type alkylcarbene complexes [214-2161. In these reactions the metallic fragment can either play the role of a ‘bulky carbonyl group’ or stabilize a given conformation of the substrate by chelate formation [2 16,2171. As in carboxylic esters it is possible to substitute alkoxy groups of Fischertype carbene complexes by non-carbon nucleophiles, such as other alcohols [73,214,218], enols [219], aliphatic amines [43,64,66,220-2241, aniline [79], imines [225], or pyrroles [226]. Strong nucleophiles can also lead to a dealkylation of methoxy-substituted carbene complexes (S,2 at the methyl group, [227]), in the same way as methyl esters can be cleaved by nucleophiles such as iodide. Carbon

36

2 Heteroatom-Substituted Curhene Complexes

nucleophiles can also attack the carbene carbon atom of Fischer-type carbene complexes to give a non-heteroatom-substituted carbene complex by substitution of the heteroatom-bearing group (Figure 2.19; see also Section 3.1). Heteroatom-substituted vinylcarbene complexes are easily prepared by aldol condensation of aldehydes with alkylcarbene complexes [228]. The latter also react readily with imidates to yield either (2-aminoviny1)- or (2-a1koxyvinyl)carbene complexes [229]. The chemical behavior of heteroatom-substituted vinylcarbene complexes is similar to that of a$-unsaturated carbonyl compounds (Figure 2.17) [206]. It is possible to perform Michael additions [217,230], 1,4-addition of cuprates [ 15I], additions of nucleophilic radicals [2311, 1,3-dipolar cycloadditions [232,233], inter[234-24 1] or intramolecular 1220,2421Diels-Alder reactions, as well as SimmonsSmith- [243], sulfur ylide- [244] or diazomethane-mediated [ 1511 cyclopropanations of the vinylcarbene C-C double bond. The treatment of arylcarbene complexes with organolithium reagents can lead via conjugate addition to substituted 1,4cyclohexadien-6-ylidene complexes 12451. Also alkynylcarbene complexes can react as Michael acceptors with nucleophiles, forming 1,3-dien-l-ylcarbene complexes (Figure 2.17). Both carbon nucleophiles, such as, e.g., enamines [246-2491, and non-carbon nucleophiles, such as imidates [250], amines [64,131,2511, aliphatic alcohols [48,79,252], phenols 12521, and thiols [252] can add to the C-C triple bond of alkynylcarbene complexes. Further reactions of the C-C triple bond of alkynylcarbene complexes include 1,3-dipolar [253,254], Diels-Alder [64,234,238,255-2581 and 12 + 21 cycloadditions [259 -2611, intramolecular Pauson-Khand reactions [43,262], and C-metallation of ethynylcarbene complexes [263]. Because of the strong electron-withdrawing effect of the M(CO), fragment, reactions of nucleophiles, dienes or 1,3-dipoles with vinylcarbene or alkynylcarbene complexes are usually faster than with the corresponding a$-unsaturated esters [242,253,264]. In addition to reactions characteristic of carbonyl compounds, Fischer-type carbene complexes undergo a series of transformations which are unique to this class of compounds. These include olefin metathesis 1206,265-2671 (for the use as metathesis catalysts, see Section 3.2.5.3), alkyne insertion, benzannulation and other types of cyclization reaction. Generally, in most of these reactions electronrich substrates (e.g. ynamines, enol ethers) react more readily than electron-poor compounds. Because many preparations with this type of complex take place under mild conditions, Fischer-type carbene complexes are being increasingly used for the synthesis 1268-2721 and modification [ 103,140,148,2731of sensitive natural products. Heteroatom-disubstituted carbenes form stable complexes with transition metals; these have not yet found broad application in organic synthesis. The use of these complexes as catalysts for various transformations is being investigated [ 153,175,274,2751.

2.2 Synthetic Applications of Heteroatom-Substitirterl Carbene Complexes OMe

OMe Nu

37

OMe

OMe R

OMe R

Fig. 2.17. Typical reactions of Fischer-type vinyl- and alkynylcarbene carbene complexes [e.g. L,: (CO),Cr].

2.2.2 Demetallation and Formation of Acyclic Products Heteroatom-substituted carbene complexes are normally rather stable compounds. Some reaction conditions, however, lead to selective demetallation of these complexes. The organic fragment can thereby be converted into different types of product (Figure 2.18). Elimination to yield alkenes can be induced thermally or by treatment with acids or bases (for one possible mechanism, see Figure 3.39) [138,206]. Less common thermal demetallations include the thermolysis of arylmethyloxy(pheny1)carbene complexes, which can lead to the formation of aryl-substituted acetophenones [276]. Further, (difluoroboroxy)carbene complexes of molybdenum, which can be prepared by treating molybdenum hexacarbonyl with an organolithium compound and then with boron trifluoride etherate at -60 OC, decompose at room temperature to yield acyl radicals [277]. Treatment of Fischer-type carbene complexes with different oxidants can lead to the formation of carbonyl compounds [ 150,2531. Treatment with sulfur leads to the formation of complexed thiocarbonyl compounds [ 1411. Conversion of the carbene carbon atom into a methylene or acetal group can be achieved by treatment with reducing agents. Treatment of vinylcarbene complexes with diborane can also lead to demetallation and formation of diols [278]. The conversion of heteroatomsubstituted carbene complexes to non-heteroatom-substituted carbene complexes

38

2 Heternatom-Substituted Curbene Complexes

k

OMe LnMH

0

LnM

+

MeOH Me0

Fig. 2.18. Typical products resulting from heteroatom-substituted carbene complexes upon thermolysis, oxidation, or reduction.

\ - MeO-

Fig. 2.19. Typical reactions of Fischer-type carbene complexes with carbanions and ylides.

is discussed in Section 3.1. Carbon nucleophiles generally react with Fischertype carbene complexes as sketched in Figure 2.19. Organolithium compounds or enolates can replace the heteroatom-bearing group, forming non-heteroatomsubstituted carbene complexes [279]. Alternatively the metallic fragment can be displaced to give enol ethers. The anionic intermediates formed from Fischer-type carbene complexes and alkynyllithium compounds are stable at -78 "C and react with aldehydes and imines to yield five-membered heterocycles [280]. Ylides, such as diazoalkanes or phosphorus ylides, can also substitute the metallic fragment of heteroatom-substituted carbene complexes. Of great synthetic potential are demetallations with simultaneous formation of CSn bonds (Figure 2.20) [ 137,146,230,281,2821. These reactions presumably proceed via a heterobimetallic intermediate containing an Sn-M-C group. Reductive elimination of the metal M from this intermediate leads to formation of the carbontin bond. The resulting alkyl- or vinylstannanes are valuable synthetic intermediates,

39

2.2 Synthetic Applications of Hetermtom-Substituted Curbene Complexes

Table 2.12. Demetallation of heteroatom-substituted carbene complexes with simultaneous C-H, C-N, and C-0 bond formation. Starting Material


OMe 1

(CO),Cr+ CH3

w(c0)3cqt BF30H-

Ph*

H,O/MeCN 1 : I , KOH (pH 12), t, 21 10 s (25 "C)

Product MeOH, MeCHO, (CO),Cr(OH)-

-40 2 eq. "C,NaBH,, MeOH, CH,C12,2h

OR

Yield

Ref.

-

(2831 [284]

76%

[I511

76%

[243]

80%

(1511

67%

(2151

QR

pyridine N-oxide, 25 "C, THF, 14 h

5

(CO),Cr

(R: 8-phenylmenthyl)

'

8

BF30H-

Ph*

(CO),Cr Q A P h

H,O, air, 23 "C, CH2CI,,24h

DMSO, 25 "C, 16h

Ph%

Qa Ph

0

40

2 Heteroatom-Substituted Curbene Complexes

Table 2.12. continued, Starting Material


OMe

Product

Yield

Ref.

96%

[253]

OMe

Ph

Ph CGO),

10

y"

DMSO, 25 "C, Id

O *'M.

Ph

% ' Me

yN

Ph

E10,C

Et0,C

hv, MeCN, 2.5 h; then 0,

Fig. 2.20. Reaction of heteroatom-substituted carbene complexes with nucleophilic and electrophilic tin derivatives.

2.2 Synthetic Applications

of

Heteroatom-Substituted Cnrbene Comple.res

41

Fig. 2.21. Photolytic generation and synthetic applications of chromium ketene complexes.

e.g. as precursors for C-radicals or organolithium compounds. Illustrative examples of some of the demetallation reactions discussed above are given in Tables 2.12 and 2.13.

2.2.3 Photochemical Transformations A remarkable reaction, discovered by McGuire and Hegedus in 1982 [292], is the photochemical conversion of heteroatom-substituted chromium and molybdenum carbene complexes into intermediates with ketene-like character (Figure 2.2 1). This reaction has been reviewed by Hegedus [203]. Photolytically generated chromium ketene complexes can acylate nucleophiles, such as alcohols [293], amines [294,295], phosphorus and sulfur ylides [296], and even arenes [73]. In addition, similar to ketenes, these intermediates undergo [2 + 21 cycloadditions with alkenes [ l o l l , imines [297,298] or aldehydes under mild conditions to yield the same type of four-membered cyclic products as would be obtained from alkoxy- or aminoketenes. Many of these reactions have also been performed intramolecularly, leading to polycyclic structures. A valuable aspect of these ketene complexes is the high diastereoselectivity with which acylations or cycloadditions sometimes occur. With the aid of chiral auxiliaries high asymmetric induction can be achieved at the newly formed stereogenic centers. By utilizing this methodology enantiomerically enriched a-amino acid derivatives [205] and other interesting molecules have been prepared, both in solution [74,299,300] and on solid support [301] (Tables 2.14, 2.15).

42

2 Heteroatom-Substituted Carbene Complexes

Table 2.13. Demetallation of heteroatom-substituted carbene complexes with simultaneous C-C and C-Sn bond formation. Starting Material


Product

CH2N2,5 "C, Et,O, < 1 min

H2C=(OM,

Yield

Ref.

93%

[287]

71%

[243]

90%

[276]

CH3

CH,Br,, LDA, -78 "C, THF

Br&

Ph

80 "C, C,H,, 2 h Ph

H

& -fpco') H

Bu,SnOTf, NEt,, Et20, 25 "C

/Y0-YSnBu3 83%

[146]

81%

[288]

75%

[289]

62%

[290]

77%

[291]

H

Bu,SnH, pyridine, 60 "C, hexane, 8 h (86% de)

CICHJ, MeLi; then H,O

(1.2 PS eq.), n B80u "C, ,

PhMe, 1.5 h

PhLSnBu3

(only Z isomer) OTBS

100 "C, C,H,

I

OMe

2.2 Synthetic Applications of Heteroatom-Substituted Curbene Complexes

43

Table 2.14. Reactions of photochemically activated chromium carbene complexes with nucleophiles. Starting Material


Product

Ph,P+CO,Bn

2 ( c 0 ) 5 c r 5

hv, C,H,

Yield

Ref.

60%

[302]

82%

12991

71%

[294]

70%

[303]

CO

MeO,C-CO,tBu (> 93% de)

(64% de) Ph

Ph

H,NXCO,Me hv, 0 "C, THF,

5

co

0 Ph

Ph

+uxCO2Me

phyy (> 95% de)

6

( C O Y r 3 (OMe

&J~~ p

hv, CO, ZnC1,

i

Ph

e

0

THF

hv, 25 "C, MeOH, 5 d

Meo&

I

I

C02Me

44

2 Heteroutom-Substituted Curhene Complexes

Table 2.15. Cycloaddition reactions of photochemically activated chromium carbene complexes. Starting Material


Product

Yield

Ref.

71%

[304]

OMe BnO

CH,

hv, 70 "C, CO, CH,CI,; then H,, Pd OMe

C0,Me

(single diastereomer) Me0 R

Ph

(co),c~+

2 0

R (R:octyl),

hv, 25 "C, CO, CH,CI,

84%

0

[I011

W I 0 (> 97% de) Me0

OH

2.2 Synthetic Applications of Heteroatom-Substituted Curbene Complexes

45

Experimental Procedure 2.2. I. Photolysis of a Chromium Carbene Complex: 2-Benzyl-4-benzyloxy-4-methyl-2,3,4,4a,7,7a-hexahy~o1H-cyclopenta[c]pyridin-3-one [294]

(CO),Cr
99: 1

-78 "C (a-ether)

Yield

cisltrans 89: 1 1

-78 "C (a-ether)

oc Cp-Fe-

Product

P 'h

-78 OC (a-ether)

A

oc \

-18 O C (a-ether)

oc

cisltrans 5O:SO

Ph

\

-78 "C (a-ether) cisltrans > 98:2

*

oc \

Cp-Fe-

od

M 'e

-18 O C (a-ether)

oc \ I

Cp-Fe=CH,

oc

50 "C (a-bromide)

cisltrans 82: 18

0

[a] All carbene complexes listed are monocationic. Treatment with HBF, (wethers) or thermolysis (a-SMe,) was used for carbene generation.

3.2 Synthetic Applications of Non-Heteroatom-SubstitutedCarbene Complexes

1 11

Table 3.2. continued. Carbene Complexla]

Substrate

oc

Conditions (Precursor)

Product

Cp- Fe=CH,

I

96%

[473]

62%

[468]

C0,Me

oc

Ref.

phXph 100 "C (&Me,)

\

Yield

C0,Me

5 yo -CO,Me

oc

l2

S0,Ph

\ Cp-Fe=CH, I

100°C

S0,Ph

(&Me,)

68%

[628]

oc

l3

Cp-Fe

I

=(

Ph/,

-65 "C (a-ether)

phq

oc oc

y

~~

l4 Cp-Fe\

od

45%

[447]

45%

[447]

66%

[I041

49%

[475]

-15 "C Ph/,

(y-allylalcohol)

% h p+

cisltrans 33:67

oc ph%

cisltrans 23 177 Ph,P

16

>i=CHZ

80 "C (a-SMe,)

CP

tempted. No asymmetric induction could be obtained with tungsten complexes and only low enantioselectivities were obtained in the cyclopropanation of E- 1phenylpropene with enantiomerically pure [Cp(CO)(Ph,P)Fe=CH,] [BF,] (generated from the corresponding chloride [483] (9% ee) or menthyl ether [458] (39% ee)). With the enantiomerically pure ethylidene complex [Cp(CO)(Ph,P)Fe=CHMe] [OTfl, however, vinyl acetate could by cyclopropanated with up to 95% ee [55,631]. Unfortunately the preparation of these resolved iron complexes is very tedious, and,

112

3 Non-Hetermtom-Substituted Carbene Complexes

also in view of the low stability of the iron carbene precursors, these reagents will probably not gain in popularity. Recent results 16321 indicate, though, that the iron complex [Cp(CO),Fe(THF)] [BF,] can be used as a catalyst for the cyclopropanation of olefins with phenyldiazomethane. The complex [Cp(CO),Fe=CHPh] [BF,] has been proposed as reactive intermediate. Thus, if enantiomerically pure, configurationally stable complexes of the type [Cp(CO)(R,P)Fe(THF)] [BF,] could be prepared, these might be useful catalysts for enantioselective cyclopropanations. Titanium Carbene Complexes A mechanistically interesting synthetic procedure for the synthesis of vinylcyclopropanes was reported in 1997 by Takeda [33] (Figure 3.34, Table 3.3). Mg, 2 P(OEt),, 20 OC MS 4 A, THF, 2 h CI CP,d CP'

'c,

&R'

R2?-R D

or SR *

RZ&R'

R2Y-sR

42-93%

I

SR

Fig. 3.34. Cyclopropanation with titanium carbene complexes generated in situ [ 3 3 ] .

The mechanism proposed for this intriguing reaction consists in desulfurization of the dithioacetal by one equivalent of the intermediate titanium(I1) complex and formation of a titanium vinylcarbene complex. [2 + 21 Cycloaddition to the alkene can lead to a titanacyclobutane intermediate which undergoes reductive elimination to yield the final cyclopropanes. The inference of a Tebbe reagent-like organotitanium intermediate is further substantiated by the report that the same reagent formed from dithioacetals and Cp,Ti[P(OEt),], olefinates ketones and esters [633] and undergoes olefin metathesis with ally1 silanes 16341 (see also [635]). This cyclopropanation reaction is indeed surprising, because titanacyclobutanes do not normally undergo reductive elimination with simultaneous formation of cyclopropanes upon thermolysis, but rather [2 + 21 cycloreversion [31].

3.2 Synthetic Applicutions of Non-Heteroatom-Substituted Curbene Complexes

1 13

Table 3.3. Cyclopropanation of alkenes with titanium carbene complexes generated in situ 1331. Dithioacetal

Alkene

Product

Yield

cishrans 2 2 7 8

ZIE 4:96

ZIE 18:82

Experimental Procedure 3.2.2. Cyclopropanation with a Titanium Carbene Complex: (E)-1-Hexyl-2-(2-phenylethenyl)cyclopropane1331

A>

Ph

+

222.37

Cp,TiCI,, Mg, P(OEt),, MS 4 A, 20 OC. THF, 6 h &Hex 112.22

228.38

A flask is charged with finely powdered molecular sieves (4 A, 50 mg), magnesium turnings (97 mg, 4.0 mmol), titanocene dichloride (249 mg, 1.0 mmol), THF (5 mL), triethyl phosphite (0.34 mL, 326 mg, 2.0 mmol) and 1octene (224 mg, 2.0 mmol), in the order given. The resulting mixture is stirred for 2 h at room temperature and a solution of 2-[(E)-2-phenylethenyl]-1,3-ditbiane (111 mg, 0.5 mmol) in THF (2 mL) is added. The mixture is stirred for 4 h and then diluted with hexane (30 mL). Filtration through Celite, concentration of the filtrate, and purification of the product by preparative TLC gives 82 mg (72%) of the title compound as a mixture of cis and trans cyclopropanes (cisltruns 60:40).

1 14

3 Non-Heteroatom-Substituted Curbene Complexes

3.2.2.2 Catalytic Cyclopropanations with Diazoalkanes Some transition metal complexes readily react with ylides to yield electrophilic carbene complexes. If these complexes can transfer the carbene to a given substrate in such a way that the original transition metal complex is regenerated then this complex can be used as a catalyst for the transformation of the ylide (carbene precursor) into carbene-derived products (Figure 3.35).

p

R

Fig. 3.35. Mechanism for the catalyzed cyclopropanation with ylides as carbene complex precursors.

Diazoalkanes are the carbene complex precursors most commonly used for the catalytic cyclopropanation of alkenes. Reactions involving this type of ylide will be discussed in this section.

Scope and Limitations: Catalysts From the mechanism sketched in Figure 3.35 it can be concluded that catalytically active complexes need a free coordination site (or a readily displacable ligand) and must act as a Lewis acid towards the diazoalkane. Some of these catalysts can, therefore, also coordinate strongly to alkenes [636]; this might lead to slight deactivation of a given catalyst if large amounts of an electron-rich olefin are present [626,637]. Strong nucleophiles (iodide, pyridine, amines, thiols) can also attenuate or completely destroy the activity of some catalysts [636]. Because of the high nucleophilicity and reactivity of diazoalkanes, catalytic decomposition occurs readily, not only with a wide range of transition metal complexes but also with Brprnsted or Lewis acids. Well-established catalysts for diazodecomposition include zinc halides [638,639], palladium(I1) acetate [6406421, rhodium(I1) carboxylates [626,643] and copper(1) triflate [636]. Copper(I1)


115

salts can also be used [644], because reduction of Cu(I1) by diazoalkanes to catalytically active Cu(1) is generally fast [636]. The complexes (CO),Cr(COD) [52,512] and [Cp(CO),Fe(THF)] [BF,] [632] have also been successfully used to catalyze cyclopropanations with aryldiazomethanes. The high cis-selectivity observed with [Cp(CO),Fe(THF)][BF,] parallels the stereoselectivity seen when stoichiometric amounts of the complex Cp(CO),Fe=CHPh+X- are used as cyclopropanating agent. The chemoselectivity of a given catalyst-carbene complex usually increases if the additional ligands become more electronegative [636]. Scope and Limitations: Substrates

The transition metal-catalyzed cyclopropanation of alkenes with diazomethane is a valuable alternative to Simmons-Smith methodology [645]. Because of the mild reaction conditions under which this reaction takes place, diazomethane is the reagent of choice if sensitive olefins are to be cyclopropanated [646-6481. Since the discovery of this reaction by Dull and Abend [617] several improved procedures have been reported. Besides copper(1) complexes, palladium(I1) acetate has become the most widely used catalyst for this reaction. For cyclopropanation of alkenes devoid of base-sensitive functional groups a ‘one-pot’ procedure has been developed [649]. In this procedure diazomethane is generated in a biphasic system from N-methyl-N-nitrosourea and potassium hydroxide in the presence of a palladium complex (e.g. Pd(acac),, (PhCN),PdCl,, or Pd[P(OPh),],) and the alkene. In this way the handling of diazomethane is elegantly avoided. In cyclopropanations with electrophilic carbene complexes, yields of cyclopropanes tend to improve with increasing electron density of the alkene. As illustrated by the examples in Table 3.5, cyclopropanations of enol ethers with aryldiazomethanes often proceed in high yields. Simple alkyl-substituted olefins are, however, more difficult to cyclopropanate with diazoalkanes. A few examples of the cyclopropanation of enamines with diazoalkanes have been reported [650]. The transition metal-catalyzed reaction of diazoalkanes with acceptor-substituted alkenes is far more intricate than reaction with simple alkenes. With acceptorsubstituted alkenes the diazoalkane can undergo (transition metal-catalyzed) 1,3dipolar cycloaddition to the olefin [651-6541. The resulting 3H-pyrazolines can either be stable or can isomerize to lH-pyrazolines. 3H-Pyrazolines can also eliminate nitrogen and collapse to cyclopropanes, even at low temperatures. Despite these potential side-reactions, several examples of catalyzed cyclopropanations of acceptor-substituted alkenes with diazoalkanes have been reported [648,655]. Substituted 2-cyclohexenones or cinnamates [642,656] have been cyclopropanated in excellent yields by treatment with diazomethane/palladium(II) acetate. Maleates, fumarates, or acrylates [642,657], on the other hand, cannot, however, be cyclopropanated under these conditions.

1 16

3 Non-Heteroatom-SubstitutedCarbene Complexes

Scope and Limitations: Diazoalkanes The limitations of cyclopropanation with diazoalkanes are mainly determined by the nature of the latter, which are hazardous to handle. The use of isolated diazoalkanes is confined to small-scale laboratory applications. Most electrophilic carbene complexes with hydrogen at Cp will undergo fast 1,2-proton migration with subsequent elimination of the metal and formation of an alkene. For this reason, transition metal-catalyzed cyclopropanations with non-acceptor-substituted diazoalkanes have mainly been limited to the use of diazomethane, aryl-, and diaryldiazomethanes (Tables 3.4 and 3.5). Some diazoalkanes cyclopropanate olefins in the absence of any catalyst [6586601. Thus, for instance, upon generation from N-cyclopropyl-N-nitrosoureaat 0 "C diazocyclopropane spontaneously cyclopropanates methylenecyclopropanes [658]. Thermal, uncatalyzed cyclopropanations of unactivated olefines with aryldiazomethanes can already occur at only slightly elevated temperatures (e.g. at 80 "C with I-naphthyldiazomethane [661]). Hence, for enantioselective cyclopropanations with a chiral catalyst, low reaction temperatures should be chosen to minimize product formation via the uncatalyzed pathway. The most common byproducts encountered in cyclopropanations with diazoalkanes as carbene precursors are azines and 'carbene dimers', i.e. symmetric olefins resulting from the reaction of the intermediate carbene complex with the diazoalkane. The formation of these byproducts can be supressed by keeping the concentration of diazoalkane in the reaction mixture as low as possible. For this purpose, the automated, slow addition of the diazoalkane to a mixture of catalyst and substrate (e.g. by means of a pump or a syringe motor) has proven to be a very valuable technique.

Stereoselectivity Cyclopropanations with diazomethane can proceed with surprisingly high diastereoselectivities (Table 3.4) [643,662-6641. However, enantioselective cyclopropanations with diazomethane and enantiomerically pure, catalytically active transition metal complexes have so far furnished only low enantiomeric excesses [650,665] or racemic products [666]. These disappointing results are consistent with the results obtained in stoichiometric cyclopropanations with enantiomerically pure Cp(CO)(Ph,P)Fe=CH,+X-, which also does not lead to high asymmetric induction (see Section 3.2.2.1).

3.2.2.3

Catalytic Cyclopropanations with Other Carbene Precursors

Sulfur Ylides Sulfonium ylides R,S=CR', [672,673] and metallated sulfones [674-6761 can cyclopropanate simple alkenes upon catalysis with copper and nickel complexes (Table 3.6). Because of the increased nucleophilicity and basicity of these ylides, compared with diazoalkanes, these reagents are prone to numerous side-reactions,

3.2 Synthetic Applications of Non-Heteroatom-Substituted Carbene Complexes

1 17

Table 3.4. Palladium- and copper-catalyzed cyclopropanations with diazomethane. Catalyst

Substrate

Conditions

Product

0

1

Pd(OAc),

dPh Et20,00C Ph

Ph

2

4

Pd(OAc),

Pd(PhCN),Cl,

Yield

Ref.

98%

[642]

97%

[641]

63%

16671

88%

[649]

100%

16641

A

COPh

A

/

O

P

h

Et,O, 0 "C

MoPh

CH2C12,Et20, KOH;(insitu CH2N2)

/d.'ph

CH2C12,Et,O,

0tPh

71%

R,N

0

II

0

0

(IR,2R)/( 1S,2s) 93:7

[663] see also [6681 ~ 9 1

R: 2-thienyl Ph

7

Ph

Ph

Ph

Et20, -15 "C

Pd(OAc), Ph

Ph

Ph

98%

[670]

68%

16551

Ph

(lS,2S)/(lR,2R) 69:31

NHBoc

OAc

NHBoc

two diastereomers 1 : I

such as Michael additions or even uncatalyzed cyclopropanations of alkenes 16771. It is probably for this reason that the reaction has not become more widely accepted in organic synthesis. From a theoretical point of view metal-catalyzed cyclopropanation of alkenes with sulfur ylides is, however, very interesting, because it nicely illustrates the chemical similarity of diazocompounds and sulfur ylides.

1 18

3 Non-Heteroutom-Substituted Curbene Complexes

Table 3.5. Transition-metal-catalyzed cyclopropanations with diazoalkanes. Diazoalkane

Substrate

Catalyst, Conditions

Product

Rh2(0Ac)4, Et20, 25 "C

Yield

Ref.

92%

[626]

92%

(6261

38%

[626]

6%

(6261

80%

[632]

56%

[671]

ph*

'OMe

cisltrans 13~87

Rh2(0Ac)4, Et20, 25 "C

Ph\njOBu cisltrans 7 1 :29

Rh2(0Ac)4, Et20, 25 "C

Ph\n/Ph cisltrans 77~23

'"\4

Rh,(OAc),,

Et20, 25 "C

Bu

cisltrans 47:53

[Cp(CO),Fe(THF)I[BF417 -78 "C, CH2CI2

ph&ph

cisltrans 96:4

Cu(OTf),, 25 "C, neat alkene O2N

Rh,(OAc),, THF

&

6%

38%

[657]

55%

[6571

CI

cisltrans 60:40 CI

Rh2(0Ac)4, THF

CI

cisltrans 84:16 CI.

CI

cisltrans 96:4

lo

N \2\

3.2 Synthetic Applicutions qf Non-Heteroutom-SubstitutedCurbene Complexes

119

Cyclopropenes As mentioned in Sections 3.1.6 and 4.1.3, cyclopropenes can also be suitable starting materials for the generation of carbene complexes. Cyclopropenone dimethylacetal [678] and 3-alkyl- or 3-aryl-disubstituted cyclopropenes [679] have been shown to react, upon catalysis by Ni(COD),, with acceptor-substituted olefins to yield the products of formal, non-concerted vinylcarbene [2 + I ] cycloaddition (Table 3.6). It has been proposed that nucleophilic nickel carbene complexes are formed as intermediates. Similarly, bicyclo[ 1.1 .O]butane also reacts with Ni(COD), to yield a nucleophilic homoallylcarbene nickel complex [680]. This intermediate is capable of cyclopropanating electron-poor alkenes (Table 3.6). Interestingly, copper(1) salts also catalyze the cyclopropene-vinylcarbene isomerization [68 11. In this case the transient carbene complexes again show electrophilic behavior, behavior similar to that of the complexes formed from copper(1) salts and diazoalkanes or sulfonium ylides.

3.2.3 C-H Insertions One of the most fascinating transformations of free carbenes, generated for instance by photolysis of diazoalkanes or by a-elimination, is their insertion into aliphatic C-H bonds. This ability of carbenes is not only of theoretical interest, but also a unique tool for the synthesis of highly strained compounds such as, e.g., bicyclo[ 1.1 .O]butanes.

3.2.3.1 C-H Insertions of Nucleophilic Carbene Complexes Some Schrock-type carbene complexes, i.e. high-valent, electron-deficient, nucleophilic complexes of early transition metals, can undergo C-H insertion reactions with simple alkanes or arenes. This reaction corresponds to the reversal of the formation of these carbene complexes by elimination of an alkane (Figure 3.36). R

C-H insertion D

Fig. 3.36. Possible mechanism of the insertion of nucleophilic carbene complexes into aliphatic C-H bonds.

I,

L,M+

alkane elimination

Y

H

As already discussed (Section 3.1.1) the elimination of, for instance, neopentane from penta(neopenty1)tantalum corresponds to an a-deprotonation of one alkyl ligand by another, the latter being eliminated as neopentane. Hence in the reverse reaction the carbene carbon atom of the (nucleophilic) carbene complex must formally deprotonate the incoming alkane with simultaneous electrophilic attack of the metal at the newly formed, carbanionic alkyl group (Figure 3.36).

120

3 Non-Heteroatorn-SubstitutedCarbene Complexes

Table 3.6. Transition-metal-catalyzed cyclopropanations with carbene precursors other than diazoalkanes. Carbene Precursor

1

ph\ S=CH, Ph/

2

ph\ ,S=CH, Ph

Substrate

Catalyst, Conditions Cu(acac),, 20"C,THF

-BU

@ O / Y

C0,Me

..(.)'

Cu(acac),, 20 "C, THF

2

Yield

Ref.

48%

[672]

45%

(6721

50%

[679]

C0,Me

C0,Me

9

Product

Ni(COD),, 40 "C, C6H6, exothermic

..C0,Me

C0,Me

cop

MeoxoMe LCO,Me

Ni(COD),, 0 "C, Et,O Me0

MeoxoMe &CO,Me

Jt*, 80%

(6781

74%

[678]

"C0,Me

Ni(COD),, 0 "C, Et,O

f

"C0,Me

Me0

cisltrans 8192

pCO,Me

,

39%

D

[680]

t

23%

il, CuCI, P(OPh),, -30 "C, 10 min

C0,Me

72%

[681] [6821


-

80 OC. C6Dl, - CMe,

-

Ti Nd

Nd

[Ti(IV), do,8 el-

AD

(Girolami, 1997)

N d C6D1f (structural proposal based on the products from aqueous hydrolysis)

- p-20 OC. C,D6 - CMe,

NP\ T',

121

- c p \ Ti -

YD

cp\T',

cd

Cd

(Hessen, 1995)

c6D5

iTi(IV), do, 16 el

RHN \ RHN-Zr-Cy RHN'

c - C ~ H 100 ~ , OC C6H12, 8 h 35%

-

-

-

NR

(Wolczanski, 1996)

RHN'

-

R = tBu,Si

RHN R,N-\,rd

-

[Zr(lV), do, 8 el NR

NR

II

RHN-V-CH3 RHN' R = tBu,Si

80 OC, 16 h

NR

II

RHtV+NR

*-,

C6H6

II

RHN-V-Ph

RHN' ,

C H (Me) c RHN-V RHN'

(Horton, 1993)

Fig. 3.37. Insertion of nucleophilic carbene and imido complexes into aliphatic and aromatic C-H bonds [408,683,689,691].

Inter- and intramolecular (cyclometallation) reactions of this type have been observed, for instance, with titanium [408,505,683-6851, hafnium 141 11, tantalum [426,686,687], tungsten [418,542], and ruthenium complexes [688]. Not only carbene complexes but also imido complexes L,M=NR of, e.g., zirconium [689,690], vanadium [69 11, tantalum [692], or tungsten [693] undergo C-H insertion with unactivated alkanes and arenes. Some illustrative examples are sketched in Figure 3.37. No applications in organic synthesis have yet been found for these mechanistically interesting processes. It should be mentioned here that nucleophilic titanium carbene complexes, generated in situ from dithioacetals and c ~ , T i [ P ( o E t ) ~(see ] ~ e.g. Sections 3.2.2.1 and 3.2.4.2), can undergo M-H insertions with silanes, germanes and stannanes [694]. This reaction represents an interesting alternative procedure for the che-

122

3 Non-Heteroatom-Substituted Carbene Complexes

mica1 modification of these important synthetic intermediates. Similarly, isolated ruthenium carbene complexes have been used to alkylate silanes by Si-H insertion [581].

3.2.3.2

C-H Insertions of Electrophilic Carbene Complexes

Carbene C-H (and Si-H, [695]) insertion is characteristic of electrophilic carbene complexes. In particular the insertion reactions of acceptor-substituted carbene complexes (Section 4.2) have become a valuable tool for organic synthesis. Few examples of C-H insertions have been reported for carbene complexes without electron-withdrawing groups attached to the carbene carbon atom [696]. Most of these are C-H insertions of cationic iron(1V) carbene complexes. Calculations performed for cyclopropanation with Fischer-type carbene complexes [28] indicate that the electrophilic attack of the carbene complex at the alkene and the final ring closure are concerted. Extrapolation from this result to the C-H insertion reaction (in which a o-bond instead of a n-bond is cleaved) suggests that C-H bond cleavage and the formation of the new C-C and C-H bonds might also be concerted (Figure 3.38).

[Fe(ll), d6, 18 e]

Fig. 3.38. Possible mechanism for the insertion of electrophilic iron(1V) carbene complexes into aliphatic C-H bonds.

However, with substrates prone to form carbocations, complete hydride abstraction from the alkane, followed by electrophilic attack of the carbocation on the metal-bound, newly formed alkyl ligand might be a more realistic picture of this process (Figure 3.38). The regioselectivity of C-H insertion reactions of electrophilic transition metal carbene complexes also supports the idea of a carbocation-like transition state or intermediate. This unique C-C bond-forming reaction has been applied to the synthesis of natural products [480,4811. In the examples reported, intramolecular C-H insertion into R,C-H groups was used for the construction of more elaborate, polycyclic carbon frameworks. Representative examples are listed in Table 3.7.


123

Table 3.7. Intramolecular C-H insertion reaction of cationic iron carbene complexes generated in situ by S-alkylation of 1 -(phenylthio)alkyl complexes (see Experimental Procedure 3.2.3). Carbene Precursor

A

Product

Yield

Reference

124

3 Non-Heteroatonz-SubstitutedCurbene Complexes

ene

The results listed in Table 3.7 might seem surprising, in that p-elimination does not seem to be a problem. In one example only (Entry 1, Table 3.7) was a small amount of the elimination product obtained. For other alkyl-substituted iron carbene complexes this elimination quickly becomes the main reaction pathway (Figure 3.14). This behavior is consistent with the generally observed trend, that olefin formation from electrophilic carbene complexes is inhibited by electronwithdrawing groups at the P-carbon, and assisted by electron donors at this position. This is because the cationic intermediate which undergoes the elimination reaction will be destabilized if the group R (Figure 3.39) is electron-withdrawing, as is the case in Helquist’s carbene complexes (Table 3.7).


1 25

-

+

H+

R

-----+Hi

Cp(Co)zFexR

I

Fig. 3.39. One possible decomposition pathway for cationic iron(1V) carbene complexes.

Hence, cationic iron carbene complexes such as Cp(CO),Fe+=CHCHZR, in which Z is an electron-withdrawing group, might also be suitable for intermolecular cyclopropanation or C-H insertion reactions. The use of such carbene complexes in organic synthesis has not yet been thoroughly investigated, but could fruitfully supplement the chemistry of acceptor-substituted carbenes.

3.2.4 Carbonyl Olefination The most useful methods for the formation of C-C bonds are based on the addition of C-nucleophiles to carbonyl compounds. Among the many variations of this basic scheme phosphorus ylides, capable of olefinating aldehydes or ketones in a single step, have proven to be exceedingly valuable reagents in organic synthesis. As discussed in previous sections, high-valent carbene complexes of early transition metals have ylide-like, nucleophilic character. Some Schrock-type carbene complexes react with carbonyl compounds in the same manner as do phosphorus ylides, namely by converting the carbonyl group into an alkene. It is particularly interesting, that some titanium and tantalum carbene complexes olefinate derivatives of carboxylic acids. These reagents are, moreover, much less basic than phosphorus ylides, and thus enable the olefination of strongly C-H acidic carbonyl compounds.

3.2.4.1 Carbonyl Methylenation In 1978 [30] Tebbe reported the preparation and characterization of the product formed from titanocene dichloride and two equivalents of trimethylaluminum (Figure 3.40). This product (‘Tebbe reagent’) is a four-membered methylene complex containing titanium and aluminum. The mechanism of its formation has been studied by Grubbs [697] (among others). Unlike phosphoranes, which normally react with ketones and aldehydes only, the Tebbe reagent methylenates a broader range of carbonyl compounds, including esters, amides, and carbonates (to yield enol ethers, enamines, and ketene acetals, respectively) [698]. Elaborate organic substrates and dicarbonyl compounds can also be methylenated in high yields with the Tebbe reagent (Table 3.8) [699-7021. Acid chlorides or

126

3 Non-Heteroatom-SubstitutedCurbene Complexes 2 AIMe,, 20 OC PhMe, 60 h 80-90%

*

CP'

'c(

Tebbe reagent

0

Fig. 3.40. Preparation and use of the Tebbe reagent for carbonyl methylenation.

2.5 eq. Tebbe reagent -40 OC to 25 "C THF/CH,CI, 2.1

1. 5 eq. rBu,Al 2. Swern oxidation

z

74%

69%

\ (Paquette, 1992)

Fig. 3.41. Ring expansion by tandem double Tebbe-Claisen methodology [699].

anhydrides are converted into titanium enolates of the corresponding methyl ketones [703]. Some nitriles can be coupled to P-ketoenamines by treatment with titanium methylene complexes [704]. An elegant ring expansion methodology has been developed by Paquette [699] (Figure 3.41). This synthetic sequence is based on the double methylenation of an a-(acy1oxy)aldehyde to give an ally1 vinyl ether, which undergoes (reductive) Claisen rearrangement when treated with trialkylalanes. Most experimental data suggest that the actual methylenating agent derived from the Tebbe reagent upon treatment with a weak base, is the highly reactive carbene complex Cp,Ti=CH, [709]. This complex is a typical Schrock-type carbene, because it is high-valent [Ti(IV)], electron-deficient (16 valence electrons) and nucleophilic at carbon. The carbonyl olefination is mechanistically closely related to olefin metathesis (Figure 3.40). [2 + 21 Cycloaddition of the carbene complex to the carbonyl

3.2 Synthetic Applications of Non-Heteroatom-SubstitutedCurbene Complexes

127

Table 3.8. Examples of methylenations with the Tebbe reagent and with dimethyl titanocene. Substrate

Reagent (Conditions)

Product

excess Tebbe reagent, 20 "C, THF, 9 h (intermediateClaisen rearrangement)

cp\ /Ti

/%

Yield

Ref.

52%

[706]

74%

[707]

68%

[708]

72%

[708]

'CH, 65 "C. THF 0 Phd0,TBS

PhdO,TBS

compound leads to a metallaoxetane which upon ring fission yields the new alkene and a metal-oxo complex. The force driving this (exothermic [710]) process is the formation of a strong M-0 double bond [397]; this renders the reaction irreversible. Hence, in contrast to olefin metathesis, which can be catalyzed by a carbene complex, in carbonyl olefination stoichiometric amounts of the organometallic reagent are required. Besides the Tebbe reagent, other types of transition-metal-based methylenating reagents have been developed. Some of these are prepared in situ from several components and the actual methylenating agent and the mechanism of its formation remain unknown. A selection of such methylenating reagents is given in Table 3.9. Some of these reagents are much easier to prepare and to handle than the Tebbe reagent, and are increasingly being used in organic synthesis. In particular the methylenation of ketones with dibromomethanehitanium tetrachloride/zinc ('Lombard0 reagent') proceeds very smoothly even with sensitive substrates, and has almost completely replaced the Tebbe reagent.

128

3 Non-Heteroutom-SubstituteclCurbene Complexes

Table 3.9. Scope and limitations of different types of methylenating reagent. Methylenating Reagent CP, A / Cp'T? /A', CI

Scope and Limitations

Reference

methylenation of aldehydes, ketones, esters, thioesters, amides, carbonates; can also induce olefin metathesis

in situ preparation: [711-7131

methylenation of aldehydes, ketones, esters, thioesters, amides, carbonates; less air-sensitive than Tebbe reagent

16981

methylenation of aldehydes, ketones; no reaction with esters

[7141

methylenation of ketones

[7 151

'Tebbe reagent' CP,Ti CP'

x

Cp,ZrCl,, Zn, CH,Br2, THF

Cp,TiCI,, Zn, CHJ,, THF Zn, TiCI,, CH,Br,, THF, CH,CI,

methylenation of aldehydes, ketones; no reaction with esters, THP-ethers, TBS-ethers, carboxylic acids, alcohols

[7 16,7171

CrCI,, CHI,, THF

conversion of aldehydes and ketones R,C=O into R,C=CHI

[7 181

conversion of aldehydes, ketones, and esters RXC=O into RXC=CHSPh

[7191

methylenation of aldehydes, ketones, esters, amides, imides, thioesters, acylsilanes, anhydrides, carbonates

[708,709,720]

Cp,TiMe,, THF or PhMe, 60-75 "C r Z n -\ B r Zn THF LZ&Br

methylenation of aldhydes and ketones

[7211

(Nysted reagent) BF,OEt,, THF, 0 "C MoOCI,(THF),, MeLi or AIMe,, THF

methylenation of aromatic aldehydes, ketones

[722-7241

3.2 Synthetic Applications of Non-Heteroatom-Substituted Carhene Complexes

129

Experimental Procedure 3.2.4. Methylenation of an Ester with Tebbe Reagent: 1-Phenoxy-1-phenylethene[712,7131 AIMe.. PhMe

0

II

198.22

Ph'

249.00

196.25

Trimethylaluminum (20 mL of a 2 M solution in toluene, 40 mmol) is added to titanocene dichloride (5.0 g, 20 mmol) under inert gas. The resulting mixture is stirred at room temperature for 3 d with evolution of methane. The mixture is then cooled to 0 "C and a solution of phenyl benzoate (4.0 g, 20 mmol) in THF (20 mL,) is added over 5 min. The resulting mixture is left to warm to room temperature within 45 min and is then diluted with anhydrous diethyl ether (50 mL). Approximately 50 drops of a 1 M aqueous sodium hydroxide solution are carefully added over 10-20 min. When gas evolution has ceased anhydrous sodium sulfate is added and the slurry is filtered through a pad of Celite. After rinsing with diethyl ether the combined filtrates are concentrated and the product is purified by column chromatography (150 g basic alumina, pentane/diethyl ether 9:l). 2.8 g (70%) of the title compound is obtained. 'H NMR (250 MHz, CDC1,) S 4.45 (d, 2.3 Hz, lH), 5.05 (d, 2.3 Hz, lH), 7.06-7.1 1 (m, 3H), 7.29-7.38 (m, 5H), 7.66-7.70 (m, 2H).

3.2.4.2 Carbonyl Olefination with Higher Alkylidenes There are unfortunately few Tebbe-type reagents capable of transferring alkylidenes other than methylene. If in the preparation of the Tebbe reagent triethylaluminum is used instead of trimethylaluminum, other types of product result [725]. Higher homologs of the Tebbe reagent can be prepared from Cp,TiCl(CH=CHMe) and diisobutylaluminum hydride [726] and the resulting reagent can be used for the olefination of ketones (Entry 3, Table 3.10). These (rather difficult-to-make) reagents have, however, not been further used in organic synthesis. Similarly, neither zirconium, tantalum, molybdenum, nor tungsten carbene complexes have been applied extensively by organic chemists for carbonyl olefination [609,727-7291, probably because of the difficulty of their preparation and the high price of some of these compounds. These reagents can, however, have appealing chemo- and stereoselectivity (Table 3.1 1). A series of reagents have been developed which are prepared in situ from a geminal dihalide or a dithioacetal [635,730] and a transition metal complex. Titanium-based reagents of this type olefinate a broad range of carbonyl compounds, including carboxylic acid derivatives (Table 3.12), and are a practical alternative to the use of isolated carbene complexes.

130


Table 3.10. Carbonyl olefination with Tebbe-type titanium reagents. Reagent, Conditions

&

Substrate

Product

Do0""'-

Yield

Ref.

55%

[731]

83%

[732]

50%

[726]

0 OC, CH,CI,, 0.5 h

Do 0"" vo

98% [733] (NMR)

\ C,H6 or PhMe, reflux

&

5

Cp-Ti CP T

/ P

h

98% [733] (NMR)

Ph

C6H6or PhMe, reflux SiMe, I

6

CP' "\Ti+SiMe, I

SiMe,

25 "C, PhMe, 1-12 h

Ph

e0 ..~ .

0x0 Ph'

23 "C, PhMe, 10 h 8

P Cp'TB CP,

50 "C, PhMe, 10-15 h

72%

[608]

83%

[605]

65%

[734]

0x0

fi I,, Ph

3.2 Synthetic Applications of Non-Heteroatom-Substituted Carbene Complexes Table 3.11. Carbonyl olefinations with nucleophilic carbene complexes. Reagent, Conditions

Substrate

Product

Yield

Ref.

[7 101 R' A

X

NP

R': Me; X: OEt; 2: 1 R': H; X: NMe,; 5:95

25 "C, Et,O or pentane

60% 77%

50%

B'zo

NP

25 "C, Et,O or pentane 3

'',pBu \PMe,Ph

"'

75 "C, PhMe, 3 h 4

cp,FBu \PMe,Ph

80%

[735]

85%

[735]

ZIE 49:s 1

Ph-BU

N 'P h n '

"'

[710]

ZIE 4753

75 "C, PhMe, 3 h N I1

OR' A

P

ROyWRO

R: CMe(CF,), Ar: 2,6-iPr,C6H3; PhMe or C,H,, 0.5-6 h

0

ukn

17361 R': Ac, 20 "C; ZIE 33:66 R': H, 20 "C; ZIE = 1 1 :89 R': H, -78 "C; ZIE < 1 :99

70% -

70%

V361 RO'

R: CMefCF,L Ar: 2,6-iPr,C,H3;

ChHhr0 . 5 4 h

R': Ac; 20 "C R': H, 20 "C; ZIE < 1 :99

0% 88%

131

132


Table 3.12. Carbonyl olefinations with carbene-complex-like reagents generated in situ. Reagent, Conditions

Substrate

Product

Yield

Ref.

88%

17371 [7 171

87%

17381

79%

[738]

64%

16331

79%

[633]

Br

ZIE 92:8

Zn, TiCI,, TMEDA, 25 "C, THF, 2 h

Zn, TiCI,, TMEDA, 25 "C, THF, 0.5 h

0". & SPh

Br

Zn, TiCI,, TMEDA, 25 OC, THF, 3 h 4

Cp,TiCl,, Mg, P(OEt13, 20 "C, THF, 3 h; then Me,C(SPh),, 5 min; then add lactone, 2 h

ZlE91.9

%Ph O

e

P

h

Cp,TiCI,, Mg, P(OEt),, 20 OC, THF, 3 h; then O PhY Ph

5 min; then add ketone, 0.5 h

6

Cp,TiCI,, Mg, P(OEt),, 20 "C, THF, 3 h; then PhCH(SPh),, 5 min; then add ester, 2 h

ZIE 53:47

o T H e x

OEt

,,THex 61%

[633]

79%

[739]

ZIE 77:23

Cp,TiCI,, Mg, P(OEt),, 20 "C, THF, 3 h; then 7

SPh M e , S i A S P h

10 min; then add lactone, 0.5 h

ZIE 56:44


133

Experimental Procedure 3.2.5. Alkylidenation of an Ester: 5-Methoxy-5undecene [737]

Arne + AB1 L," TiCI,,TMEDA,Zn

Bu

117.17

243.97

184.32

To THF (10 mL) at 0 "C under inert gas are added, in this order, titanium tetrachloride (4 mL of a 1 M solution in dichloromethane, 4 mmol), TMEDA (1.2 mL, 0.93 g, 8.0 mmol), and zinc dust (0.59 g, 9.0 mmol). The resulting mixture is stirred at 25 "C for 30 min and a solution of methyl pentanoate (0.12 g, 1.0 mmol) and 1,l-dibromohexane (0.54 g, 2.2 mmol) in THF (2 mL) is added. The dark mixture is stirred at 25 "C for 2 h, cooled to 0 "C, and treated with potassium carbonate (1.3 mL of a saturated aqueous solution). After stirring for a further 15 min at 0°C ether (20 mL) is added and the resulting mixture is filtered through a short column of basic alumina (activity 111) using etherhiethylamine (200: 1, 100 mL). Concentration of the filtrate and column chromatography (basic alumina, pentane) gives 0.18 g (96%; Y E 91:9) of the title compound. I3C NMR (CDCI,, 2 isomer) 6 13.9, 14.1, 22.3, 22.6, 24.7, 29.4, 29.8, 31.1, 31.6, 56.4, 110.1, 155.0.

Experimental Procedure 3.2.6. Alkylidenation of a Ketone: 4-Methyl-1-phenylocta-1,3-diene [633] MS 4 A, Mg, Cp,TiCI,, P(OEt),L

100.16

222.37

phL 200.33

A, 150 mg), magnesium turnings (43 mg, 1.8 mmol), titanocene dichloride (374 mg, 1.5 mmol), THF (4 mL), and triethyl phosphite (0.51 mL, 2.9 mmol) is stirred under argon at room temperature for 3 h. A solution of (E)-2-(2-phenylethenyl)-1,3-dithiane (122 mg, 0.55 mmol) in THF (1 mL) is added, followed after 5 min by dropwise addition of a solution of 2-hexanone (50 mg, 0.50 mmol) in THF (2.5 mL). The resulting mixture is stirred at room temperature for 30 min, diluted with hexane (30 mL), and filtered through Celite. Concentration of the filtrate and purification of the crude product by preparative TLC (hexane/ethyl acetate 98:2) yields 74 mg (74%; W E 60:40) of the title compound. A mixture of finely powdered molecular sieves (4

134


"

1 'TiCp,

* H

(Nicolaou, 1996)

rn0Jh+ a0Jh - 2

0

RO-Mo,

Rd

3Ph

ROH = (CF,),MeCOH

(Grubbs, 1993)

Fig. 3.42. Tandem alkene metatheses-carbonyl olefinations [740-7421.

One remarkable application of carbene complexes is the combination of olefin metathesis with carbonyl olefination. If a given substrate has both C-C and C-0 double bonds, it might be possible to realize with a given carbene complex olefin metathesis to yield a new carbene complex, followed by an intramolecular carbonyl olefination step. As emphasized above, because of the irreversibility of the carbonyl olefination, stoichiometric amounts of carbene complex will be required. Figure 3.42 shows some examples of such tandem-metathesis-olefination reactions.

3.2.5

Olefin Metathesis

Olefin metathesis refers to a process in which two alkenes exchange their alkylidene fragments. This reaction has recently been reviewed [743 -7471. An exciting account on the discovery of olefin metathesis has been written by Eleuterio [748].

3.2 Synthetic Applications of Non-Heteroutom-SubstitutedCarbene Complexes

135

4 eq. Tebbe reagent reflux, THF D

0 H

OBn

61%

H OBn

(Nicolaou, 1996)

OBn

Fig. 3.42. continued.

Streck has discussed economic and ecological aspects of the industrial application of this reaction [749]. A thorough discussion of the subject is to be found in a monograph by Ivin and Mol [750].

3.2.5.1 General Considerations Olefin metathesis reactions have been grouped into the different categories shown in Figure 3.43. The metallacyclobutane mechanism of olefin metathesis has been discussed in Sections 1.3 and 3.1.7. For metathesis of acetylenes carbyne complexes are generally required (Figure 3.44), and both heterogeneous and homogeneous catalytic systems have been developed for this purpose. Homogeneous, single-component catalysts such as, e.g., W(=CCMe,)(OCMe,), or W(-CMe)(OCMe2CF3),, cannot only be used for exchange metathesis of alkynes but also for ROMP of cycloalkynes, ADMET of a,o-diynes, and RCM of a,odiynes [75 I]. When alkynes are treated with catalytic amounts of a carbene complex, polymerization instead of metathesis can occur (Figure 3.44) [565,595,597,752-7541. The use of carbene complexes to catalyze alkyne polymerization enables much better control of the reaction than with heterogeneous or multi-component catalysts. Pure acetylene oligomers (n = 3-9) with terminal tert-butyl groups have been prepared with the aid of a tungsten carbene complex [755].

136

3 Non-Heteroatom-SubstitutedCurbene Complexes Exchange metathesis

Self metathesis (degenerate)

Self metathesis (productive)

-

2

2

A

./ +

m+./

-

Bu Cross metathesis

2

-

Ph-ph

Bu P

P

h

Ring-openingmetathesis polymerization (ROMP) r

1

H

n

Fig. 3.43. Types of olefin metathesis reaction.

Industrial Applications

In contrast with other types of carbene complex reaction discussed in this book, which mainly are tools for the synthesis of fine chemicals, the development of olefin metathesis was essentially driven by the petrochemical industry. The first examples of this reaction were the polymerization of norbornene and the metathesis of propylene to 2-butene and ethylene, described by Eleuterio [756] and Peters [757]. The catalysts initially used for exchange metathesis were supported metal oxides, such as MoO,/Al,O, or WO,/SiO,, and temperatures as high as 500 "C were necessary. The first catalysts for ring-opening polymerization were Ziegler-Natta-type catalysts (TiCl,/AIR,).


131

Ring-closing metathesis (RCW

Acyclic diene metathesis (ADMET)

Fig. 3.43. continued.

/

r

1

Fig. 3.44. Reactions of carbyne and carbene complexes with alkynes.

As early as 1966 Phillips Petroleum Co. began to operate a 50 000 t/y metathesis plant in Canada, producing 2-butene and ethylene from propene (Phillips Triolefin Process). Currently, the most important industrial application of olefin metathesis is probably the 'Shell Higher-Olefin Process' (SHOP, Figure 3.45). In this process ethylene is first oligomerized under nickel catalysis to a mixture of C, to C,, terminal alkenes. The desired C,-C,* fraction is separated by distillation and further used as copolymer for polyethylene production, or is hydroformylated and reduced to detergent alcohols. The undesired oligoethylene fractions (< C, and > C,8) are mixed and isomerized with an alkali metal-based catalyst to internal alkenes. These are subjected to repeated exchange metathesis (100-125 "C, supported oxide catalyst) 10-1 5 % of the desired detergent-range alkenes being obtained per pass. Alternatively, cross metathesis with ethylene can be used to produce terminal alkenes of lower molecular weight. The world-wide capacity for the Shell higher-olefin process reached lo6 tly in 1990.

138


// NilPR,

I

oligomerization

metathesis detergents polymers

-

1

distillation c6-c18

*

Fig. 3.45. Schematic representation of the Shell higher-olefin process (SHOP).

Further important industrial applications of olefin metathesis include the synthesis of 3,3-dimethyl-1-butene (‘neohexene’, intermediate for the production of musk perfume) from ethene and 2,4,4-trimethyl-2-pentene, the manufacture of a,o-dienes from ethene and cycloalkenes (reversed RCM), and the ROMP of cyclooctene and norbornene to VestenamerB and NorsorexB, respectively.

3.2.5.2 Heterogeneous Catalysts Because of the importance of olefin metathesis in the industrial production of olefins and polymers, many different catalysts have been developed. Almost all of these are transition metal-derived, some rare exceptions being EtAlCl, [758], Me,Sn/A1,03 [759], and irradiated silica [760]. The majority of catalytic systems are based on tungsten, molybdenum, and rhenium, but titanium-, tantalum-, ruthenium-, osmium-, and iridium-based catalysts have also proven useful for many applications. The known catalyst systems for olefin metathesis can be grouped into heterogeneous catalysts, homogeneous multi-component catalysts, and homogeneous single-component catalysts. Heterogeneous catalysts are mainly used for gas-phase olefin metathesis in industrial production plants. These catalysts consist of a support (A1,0,, TiO,, Nb,O,, SiO,, etc.) which provides mechanical stability and a high surface area (> 200 m2 g-I), but can also have a decisive influence on the activity of the final catalyst. The support is mixed or impregnated with 1-20% of either a transition metal oxide or another metal derivative (see Table 3.13) [761,762]. Activation by treatment with H, [763,764], 0, [765-7671, CO [768], or HC1 at high temperatures [769] is usually necessary to obtain efficient catalysts. Activation can also be achieved by photolysis [764,766] or by treatment of the supported metal derivative with lower alkyl cyclopropanes [766,768]. It is assumed that the activation step generates free coordination sites or carbene complexes. Cyclopropanes are

3.2 Synthetic Applications of Non-Heteroatom-SubstitutedCurbene Complexes

139

believed to undergo oxidative insertion with the support-bound metal to yield metallacyclobutanes, which decompose into ethylene and a carbene complex by [2 + 21 cycloreversion [768]. Many heterogeneous and homogeneous metathesis catalysts require a so-called cocatalyst, such as BuLi, EtAlCl,, R,Sn [770], or R,Pb [771], for which several possible functions are being discussed. Organolithium compounds can react directly with the transition metal derivative to yield catalytically active carbene complexes (see Section 3.1.1). Alternatively, metal oxides can be reduced by the cocatalyst, generating free coordination sites. One further possibility is the formation of a metal-cocatalyst complex, which becomes the actual catalyst. This last option is probably the case for AlX,R,, "), as the activity of the resulting catalysts usually increases with increasing Lewis-acidity of the aluminum derivative used. Generally the activity of heterogeneous catalysts for olefin metathesis increases with its Lewis acidity [772]. Some heterogeneous and homogeneous metathesis catalysts also require promoters or additives, such as water, alcohols, or alumosilicates. Table 3.13. Heterogeneous catalysts for alkene metathesis.

6

7

Catalyst

Temperature

Substrate

MOO,, PTiO,, Me,Sn

25 "C

propen e

MOO,, SiO,

20 "C

propene

Mo(CO),, S O ,

27 "C

propene

Mo,(OAc),, SiO,

25 "C

propen e

WC1,(2,6-Br,C6H@),, NbO,, SiO,, iBuAIC1,

20 "C

2-pentene

WCI(CO),Cp, SiO,, iBuAICI,

20 "C

2-pentene

140 "C

1-butene

Re2%

8

Re,O,, AI,O,, PbEt,

35 "C

I-hexene

9

MeReO,, SO,, AI,O,

20 "C

2-pentene

10

polystyrene-bound (RCy,P),CI,Ru=CHCH=CPh,

20 "C

cis-2-pentene

Reference

140


Table 3.14. Examples of multi-component catalysts for homogeneous-phase alkene metathesis. Catalyst

Temperature

Substrate

Reference

(Ar: 2,6-iPr,C,H3) 2

WCI,, Bu,Sn

30 "C

norbornene

3

WCI,, Et,AI,CI,, PhNH,

20 "C

propene

4

WOC1,(2,6-Br,C6H,O),, PbEt,

120 "C

2-alkenes

5

W(2-MeC6H,O),Cl,, Et,AI,CI,

20 "C

I-octene

6

WOCI,, EtAICI,

20 "C

2-pentene

V911

25 "C

cyclooctene

13931

20 "C

dicyclopentadiene

[792,793]

8

+ N,CHCO,EI

3.2.5.3 Homogeneous Catalysts Small-scale preparations and the chemical modification of fine chemicals and elaborate intermediates are usually conducted in solution. For this purpose soluble metathesis catalysts of predictable and reproducible activity are generally preferred. The catalytic systems presently known can be grouped into multi-component and single-component catalysts (Tables 3.14-3.16). Although the applications of Fischer-type carbene complexes are discussed in Chapter 2, their use as catalysts for olefin metathesis (a minor aspect of the chemistry of these compounds) will be discussed in this section. Low-valent, 18-electron carbene complexes (Fischer-type) are electronically and coordinatively saturated and must usually be activated to become efficient metathesis catalysts. This activation can be effected by thermal or photolytic [781,782] removal of one ligand, e.g. carbon monoxide, or by treatment with a Lewis acid (Table 3.15) [783]. High-valent, electron-deficient carbene complexes can either require activation (e.g. by a Lewis acid) to catalyze metathesis (Table 3.14) or not require any


14 1

Table 3.15. Fischer-type carbene complexes as catalysts for homogeneous-phase alkene metathesis. Catalyst

Temperature, Activator

Substrate

Reference

1

[(CO),Mo=C(O)Ph][NBu,], MeAICI,

-

styrene

WI

2

(CO),W=C(Ph),

40 OC

cycloalkenes, internal alkenes

[795,796]

3

(CO),W=C(OMe)Ph

50 "C

norbornene, cyclobutene, alkynes

[797,798]

4

(CO)5W=C(OMe)Ph

PhCgH

cyclopentene

[7991

5

(CO),W=C(OMe)Ph

hv

COD

[78 11

25 "C

norbornene

[goo1

6

+ AICI,

further activation (Table 3.16) [606]. Some of the known (Schrock-type) carbene complexes, which catalyze alkene metathesis without any further additive, have proven to be exceedingly efficient catalysts. These complexes can initiate ROMP at high rates, thus generating growing polymer chains of similar lengths. As the chaincarrying alkylidene complexes undergo practically no terminating side-reactions [22,396,604,784,785] some of these catalysts are able to induce living polymerization, and thus enable the production of polymers with very narrow molecular-weight distributions. The length of the polymer chains can be controlled by the amount of catalyst used and also by deliberate termination of the polymerization after a certain time. This can, for instance, be achieved by addition of an aldehyde, which reacts irreversibly with the carbene complex. Unlike in radical or anionic polymerizations, in ROMP with single-component metathesis catalysts the growing polymer chain remains able to further grow even after consumption of the monomer. This enables the manufacture of block copolymers with interesting physicochemical properties by sequential addition of different monomers to such 'living' systems. Most known single-component catalysts can be easily modified by simple ligand exchange; this enables precise fine-tuning of the activity and the stereochemical output of a given catalyst.

142


Table 3.16. Alkylidene and carbyne complexes as single-component catalysts for homogeneous-phase alkene metathesis. Catalyst

Temperature

Substrate

Reference

15 "C

cis-2-pentene

[6 161

-

norbornene

W1

20 "C

cyclopentene

[8021

20 "C

norbornene, dicyclopentadiene

[427]

20 "C

2-pentene

40 "C

norbornene

[go31

80 "C

dicyclopentadiene

[804,805]

(Ar:2,6-iPr2C,H,) 2

Me,Si7 /-TaMe,Si

S ,M i e,

'SiMe,

4

R0.d

Ro'

NPh LSiMe,

ROH: (CF,),MeCOH generated by hv-induced elimination of TMS from the dialkyl complex 5

4, ROH: (CF,),MeCOH

6

The optimum catalyst for a given reaction depends primarily on (a) the energetics of the reaction and (b) the functional groups present in the substrate. If, for instance, a strained cycloalkene such as norbornene or cyclobutene is to be polymerized, a catalyst of low activity will be sufficient to attain acceptable reaction rates. RCM

143


can often also be accomplished with catalysts of low activity, in particular when five- or six-membered rings are formed and the equilibrium is continuously shifted by removal of one of the products (e.g. ethylene). Highly active catalysts will, on the other hand, be required when acyclic or highly substituted olefins have to be metathesized effectively. If olefin metathesis is to be conducted in solution, solvents of low Lewis-basicity will generally give the best results (CH,Cl, > toluene > THF). As discussed above, metathesis is initiated by the formation of a n-complex between the metal and the alkene. Hence, other nucleophiles will compete with the alkene for these coordination sites and in some systems even THF can lead to complete deactivation of the catalyst [786]. Tungsten-based catalysts which can even metathesize ally1 thioethers have, however, been described [787].

3.2.5.4 Scope and Limitations of Molybdenum- and Ruthenium-Based Homogeneous Catalysts Because of the enormous synthetic potential of molybdenum- [22] and rutheniumbased [57,806] single-component catalysts, a closer look at the scope and limitations of the most promising compounds known to date is appropriate. The systematic exploration of the synthetic possibilities offered by these new catalysts has just begun, and many new developments are to be expected in the near future 1744,746,747,8071. As quick reference for the organic chemist, the most relevant chemical properties of two types of frequently used catalyst (Figure 3.46) are listed below. These carbene complexes are quite robust and well-suited to the metathesis of elaborate organic intermediates.

I

k'

N

.

(CF,),MeCO -M , o& ( C(CF,),MeCO F , ) , M e C O/- l ? \lox

Fig. 3.46. Suitable catalysts for homogeneous-phase olefin metathesis.

lI

\ / R

R = Me, Ph

R' = Ph, CH=CPh,

A

B

Metathesis Activity Molybdenum complexes A (Figure 3.46) react efficiently with terminal and internal alkenes in toluene (e.g. 500 eq. Z-2-pentene are metathesized in 2 min at 25 "C; 20 eq. of styrene in 2 h at 25 "C). These catalysts also oligomerize 2,4-hexadiene [808] and 1,5-hexadiene [809] and promote RCM of enol ethers. Isomerization of alkenes by catalysts A is a potential catalytic side-reaction [810-8121.

144

3 Non-Heteroatorn-Substituted Curbene Complexes

Ruthenium complexes B also undergo fast reaction with terminal alkenes, but only slow or no reaction with internal alkenes. Sterically demanding olefins such as, e.g., 3,3-dimethyl- 1-butene, or conjugated or cumulated dienes cannot be metathesized with complexes B. These catalysts generally have a higher tendency to form cyclic oligomers from dienes than do molybdenum-based catalysts. With enol ethers and enamines irreversible formation of catalytically inactive complexes occurs [582] (see Section 2.1.9). Isomerization of ally1 ethers to enol ethers has been observed with complexes B [582].

Stability and Reactivity towards Functional Groups Although solutions of molybdenum complexes A in methylcyclohexane or benzene are stable for several weeks at room temperature [416], these complexes are sensitive towards oxygen and protic solvents [8 13,8141. Aldehydes are quickly olefinated by complexes A, whereas variable reactivity is observed towards ketones [416,736]. With carboxylic esters usually no reaction occurs. Ruthenium complexes B are stable in the presence of alcohols, amines, or water, even at 60°C. Olefin metathesis can be realized even in water as solvent, either using ruthenium carbene complexes with water-soluble phosphine ligands [8151, or in emulsions. These complexes are also stable in air [584]. No olefination of aldehydes, ketones, or derivatives of carboxylic acids has been observed [582]. During catalysis of olefin metathesis replacement of one phosphine ligand by an olefin can occur [598,809]. The increased stability of ruthenium carbene complexes towards oxygencontaining compounds might be because later transition metals, having more d-electrons, are softer and hence react better with soft bases, e.g. olefins. The early transition metals, on the other hand, having few d-electrons, are generally harder and react preferentially with hard bases, such as water or carbonyl compounds. 3.2.5.5

Ring-Opening Metathesis Polymerization (ROMP)

The mechanism of ROMP is sketched in Figure 3.47. Because of the high demand for new polymers with improved properties, ROMP has received much attention since the discovery of olefin metathesis [396,816,817]. One of the first applications envisioned of ROMP was the preparation of polyenes with rubber-like properties by ROMP of cyclopentene. Although this polymer did not have the optimum product profile, the polymer obtained by ROMP of cyclooctene can indeed be used in blends with other rubbers, conferring on the final product improved mechanical properties and simplifying its processing. This polymer, called Vestenamer 8012, is being produced by Chemische Werke Huls, Marl, Germany, and the annual capacity in 1990 reached 12 000 t. Comparison of the energetics of ROMP for the series of homologous lower cyclic alkenes (Table 3.17) suggests that three-, four-, and eight-membered and larger rings, should be polymerizable, because AG for ROMP of the parent compounds is negative. Because the free energy of the polymerization of five- to seven-membered

3.2 Synthetic Applications of Non-Heteroutom-Substituted Carbene Complexes

145

Initiation

Propagation

R'

Termination

Fig. 3.47. Mechanism of ring-opening metathesis polymerization catalyzed by carbene complexes.

Table 3.17. Thermodynamic parameters for the conversion of liquid monomer into solid amorphous polymer [750]. Monomer

Cyclobutene Cyclopentene Cyclopentene Cyclohexene Cyclohexene Cycloheptene Cyclooctene Cycloocta-I ,5-diene Cycloocta-l,5-diene Norbomene

Polymer

Z Z E Z E

70% E 48% E Z E 45% E

AHo (kJ mol-') -121 -15.4 -18 2 -2 -18

-13 -25 -3 3 -62.2

As0 (kJ mol-') -52 -51.8 -52 -3 1 -28 -31 -9 -5 -5 -50

AGO (25 O C ;

(kJ mol-') -105 -0.3 -2.6 6.2

1.3 -1 -13

-19 -24 -47

rings is, however, close to zero or positive, such compounds might not polymerize upon treatment with a metathesis catalyst. Additional substituents, and the reaction conditions can, however, have a decisive impact on ROMP. Subtle effects can operate, and it is often not possible to predict whether or not a system will undergo ROMP (Figure 3.48). As for other types of polymerization, ROMP can only be initiated if the concentration of monomer reaches a certain value and the temperature does not exceed a given limiting value. Hence, polymerization occurs more readily at high

146

3 Non-Heteroatom-SubstitutedCarbene Complexes Cycloalkenes which undergo ROMP SiMe,

0

Q

0%

Q

R

Cycloalkenes which do not undergo ROMP

,,XPh

p p ro EtO

Fig. 3.48. Selection of cycloalkenes and their suitability for ROMP [750,8181.

monomer concentrations and at low temperatures. Interesting reaction sequences have been realized by adjustment of these two parameters. It is, for instance, possible to prepare cyclopentenes by ring-closing metathesis of a 1,6-heptadiene at high temperature in solution, and then polymerize the cyclopentene by ROMP at a lower temperature and at high concentration [8 121. Further interesting applications of ROMP include the preparation of conjugated polyenes by oligomerization of synthetic equivalents of cyclobutadiene [819] or 1,6methanobenzene [8 161. With the discovery of ruthenium carbene complexes, which can catalyze ROMP in the presence of air and water [584,820], ROMP could be extended to hydrophilic


of Non-Heteroatom-Substituted Carbene

Complexes

147

cycloalkenes. Carbohydrate-substituted polymers have been prepared by ROMP of norbornene or 7-oxanorbornene derivatives in water [821-8241. Several norbornenes substituted with biologically relevant molecules (e.g. nucleotides [825], amino acid derivatives [826], p-lactams [827]) or other functionalities, such as, e.g., N,N-dipyridylcarbamoyl groups as chelating ligands [828], have also been successfully polymerized [8 16,829,8301. Polymers produced by ROMP are generally equilibrium mixtures of a highmolecular-weight fraction of linear polymers (mwt > lo5 g mol-') and a lowmolecular-weight fraction of cyclic oligomers. In addition to these two components, the polymer can also contain different amounts of other polymers, produced by a different polymerization mechanism (Figure 3.49). This can become a serious problem with very reactive monomers. For instance, ROMP of norbornene with ReCl(CO)S/EtAICl, at 100 "C yields 98.6% of ring-opened product. At llO"C, however, only 5.1% of the ROMP-product but 94.9% of the ZieglerNatta-polymerization-product (poly-2,3-norbornylene) are obtained [83 11. Similar behavior has been observed with cyclobutene [750, p 2601.

ROMP t

Q

w

Fig. 3.49. Types of product arising from olefin polymerization with metathesis catalysts.

Stereoselectivity

The stereochemistry of polyenes formed by ROMP depends on the monomer used, on the catalyst, and also on the solvent [812]. ROMP tends to yield predominantly Z-polyenes when catalysts with several sterically demanding or chelating ligands are employed (see e.g. [832]). If, on the other hand, the transition metal bears few or small ligands, the stereochemistry of the polyene will depend mainly on the 1,2and 1,3-interactions of the C-substituents on the intermediate metallacyclobutanes. Depending on the monomer used, either 2- or E-polyenes may be obtained with steriplly nondemanding catalysts. An exhaustive review of the stereochemical outcome of the ROMP of different mono- and polycyclic alkenes is given by Ivin and Mol [750].

148

-


\

RCM and ADMET of dienes

RCM of enynes

Fig. 3.50. The mechanism of ring-closing metathesis of dienes and enynes.

3.2.5.6 Ring-Closing Metathesis (RCM) When dienes are subjected to olefin metathesis, either oligomerization (ADMET) [808,809,833-8371 or cyclization (RCM) can occur [743,747,807] (Figure 3.50). Scope and Limitations

As in other types of metathesis it is mainly thermodynamic factors which determine whether ADMET or RCM becomes the preferred reaction pathway. Because of the strain of three-, four-, and eight- to eleven-membered rings, these will be difficult to prepare by metathesis. Five- and six-membered rings, on the other hand, are readily formed [838,839], and it might not be possible to polymerize 1,6- or 1,7-dienes, even in the absence of a solvent. Generally low substrate concentrations and high temperatures will increase the ratio RCM/ADMET. Also additional substituents at the diene backbone, which force the diene into an appropriate conformation, can lead to a negative AGO for RCM. Some common 'tricks' for achieving this are the

3.2 Synthetic Applications of Non-Heternatom-SubstitutedCarbene Complexes

149

Fig. 3.51. Common catalysts for homogeneous-phase olefin metathesis.

introduction of gem-dimethyl groups or rings (e.g. 1,2-phenylene) between the two C-C double bonds to be ligated. Macrocyclic lactones [840-8501, lactams [842,85 11, carbamates [852], pyridinium salts [853], ethers [811,854-8581, peptoids [859-8641, and calixarenes [865] can also be prepared by RCM. As in other macrocyclizations, yields can usually be improved by lowering the concentration of the reactants. Macrocyclization of esters of allylglycine with diols has been successfully used to prepare derivatives of 2,7-diaminosuberic acid [86 1,8641. The latter are surrogates of cystine, and therefore of interest for the preparation of peptide mimetics. For unknown reasons protected allylglycine derivatives can not be directly ‘dimerized’ by self metathesis [864]. However, catechol [864], ethylene glycol [861J, and 1,2- or 1,3-di(hydroxymethyl)benzenederivatives [860] of allylglycine are suitable templates for the formal self metathesis of this amino acid via RCM. One drawback of RCM-based macrocyclizations is the formation of EIZ-isomeric mixtures. Because high yields are often obtained, however, and the experimental set-up is simple, RCM is an attractive route to macrocyclic compounds. Also in macrocyclizations the conformation of the starting diene has an influence on the RCMIADMET ratio. Substituents on the diene which form hydrogen bonds between each other or with the intermediate carbene complex, or external Lewis acids can have an important effect on the course of the reaction. Such effects, often subtle, might explain the variable results sometimes obtained in macrocyclizations [842], but make synthesis-planning and the formulation of general guidelines difficult. Particularly interesting is the reaction of enynes with catalytic amounts of carbene complexes (Figure 3.50). If the chain-length between olefin and alkyne enables the formation of a five-membered or larger ring, then RCM can lead to the formation of vinyl-substituted cycloalkenes [866] or heterocycles. Examples of such reactions are given in Tables 3.18-3.20. It should, though, be taken into account that this reaction can also proceed by non-carbene-mediated pathways. Also Fischer-type carbene complexes and other complexes [867] can catalyze enyne cyclizations [267]. Trost [868] proposed that palladium-catalyzed enyne cyclizations proceed via metallacyclopentenes, which upon reductive elimination yield an intermediate cyclobutene. Also a Lewis acid-catalyzed, intramolecular [2 + 21 cycloaddition of, e.g., acceptor-substituted alkynes to an alkene to yield a cyclobutene can be considered as a possible mechanism of enyne cyclization.

150

3 Non-Heter~)atom-SubstitutedCurbene Complexes

The most commonly used catalysts for RCM are the three carbene complexes sketched in Figure 3.5 1. The order of reactivity of these three catalysts towards alkenes (but also towards oxygen) is 1 > 3 > 2. As illustrated by the examples in Table 3.18, these catalysts tolerate a broad spectrum of functional groups. Highly substituted and donor- or acceptor-substituted olefins can also be suitable substrates for RCM. It is indeed surprising that acceptor-substituted alkenes can be metathesized. As discussed in Section 3.2.2.3 such electron-poor alkenes can also be cyclopropanated by nucleophilic carbene complexes [34,678] or even quench metathesis reactions [34]. This seems, however, not to be true for catalysts 1 or 2. Molybdenum catalysts such as 1 can also lead to the isomerization of alkenes [810-8121. Care is due in particular if enantiomerically pure olefins with the stereogenic center near the C-C double bond are to be metathesized, or when strained rings are to be formed [81 I]. The most critical cyclization reactions are those in which tetrasubstituted alkenes or eight- to eleven-membered rings are formed [845,869]. Particularly interesting is Entry 38 in Table 3.18, a tandem ring-openinghing-closing metathesis. In this reaction ring-opening metathesis of the norbornyl group leads to the formation of a carbene complex, nicely disposed to undergo RCM with a vinyl group to yield a cyclooctene. A selection of preparations of carbocyclic compounds by RCM is given in Table 3.18.

3.2 Synthetic Applications of Non-Hetert,utom-Substituted Carbene Complexes

15 1

Table 3.18. Formation of cycloalkenes by ring-closing metathesis. Substrate'"

Conditions

2% W(O)C1,(2,6Br2C,H,O),, 4%PbEt,, 9 0 ° C C6H3C13' OTBS

A E E

5

9

m

Yield

9

5% 1,65 "C, C,H,, 24 h; (5%yield with3)

4% 1, 20 "c, C,H,, 15 min

oG

CH2C12, 6%3,20°C, 12 h

[a] E: C0,Et

70% [771] I8 121

(undergoes ROMP; 5 M in DME, -30 "C, 0.3% 1 )

89% [814]

EEpOH OH

6% 1,20 "C, pentane, 3.5 h

E

Ref.

2% W(O)C1,(2,6Br2C,H30)2, 4%PbEtd,90"C, PhMe., 1 h

5% 3,20 "C, CH2C12,24 h; (no reaction with 1)

H O &

6

*

COzMe

Product

97%

[814]

84%

[741]

88% [871]

flAo To1

55% [872]

152

3 Non-Heteroutom-SubstitutedCurbene Complexes

Table 3.18. continued. Substrate"'

4% [RuCI,(CO),],, 80 "C, CO, PhMe, 4 h

10

11

Conditions

:q SiMe,

c /Jp

79% [873]

80% [873]

TBSO

93% [867]

OSiEt,

15% 2, 100 "c, PIiMe, 1.5 h

14

2% 1,20 "C, CH,CI,, 15 rnin

h-$,

Ref.

WPh

4% PtCI,, 80 "C, PhMe, 1 h

OSiEt,

13

Yield

4% [RuCI,(CO),],, 80 "C, CO, PhMe, 1 h

TBSO

12

Product

(9

78% [874]

85% (7411

DCH0 DCHO 82% [813]

15

4

5% 3 , 2 0 "C, CH,CI,, 24 h

97% [814]

17

5% I, 65 O C , C6H6,24 h; (no reaction with 3)

61% [814]

18

5% 3,20 "c, CH,CI,, 24 h

16

/

96% [814]

3.2 Synthetic Applications cf Non-Heteroatom-SubstitutedCarbene Complexes Table 3.18. continued. Substrate'"

Conditions

Product

Yield Ref.

91%

C0,Me

22

23

F

O

B

[876]

C0,Me

,

@

13% 1, 20 "C, pentane, 3 h

80% [871]

(CO),W=C(OMe)Ph, 1%

75 "C, PhMe, 18 h /

/

0.25% 1, 25 "C, neat, 1 h

95%

[880]

153

154


Table 3.18. continued. Substrate'"'

Conditions

Product

Yield Ref. 62%

5% 1 , 4 0 "C,

[844]

CO,, 72 h OBn

10% 2, KO "C,

C6H6,35 h; (only ADMET with 1)

29

E

BnoDoB" 40% [881]

E

96% [814]

5% 3 , 2 0 "C, CH,CI,, 4 d

5% 1 , 6 5 "C,

31

96% (8141

C6H6924h; (25% yield with 3)

8% MTO on Si02/AI,0,, 40 "C, FCI,CCF,CI, CH,CI,, 7 d

4% 2,20 "C, C6H,, 24 h

33

Me0 HO

36

[882]

99% [882]

2%3,8OoC,17h, I ,2-dichloroethane

34

35

58%

63%

[877]

HO

5% 2,25 "C,

C6H6,4 h

3% 1, 55 "c, hexane, 3 h; then TBAF

75% [883]

92%

[869]

3.2 Synthetic Applications of Non-Heteroatom-Substituted Curbene Complexes

155

Table 3.18. continued. Substratel'l

38

Conditions

Product

Yield

Ref.

ethylene, 8% 1, CH2CI2,25 "C

for 1 h. The mixture is left to cool to room temperature and filtered through a ca. 3 mm bed of silica gel. After rinsing with toluene (50 mL) the combined filtrates eous sodium hydroxide solution (1%, 15 mL) and then with are washed with water (15 mL). Concentration and distillation (62-66 'C, 15 Tom) yields 12.0g f the title compound as a colorless liquid. 'H NMR (300 MHz, CDCI,) , 3.02 (s, 4H), 4.19 (9,7 Hz, 4H), 5.62 (s, 2H); 13C NMR

14.06, 40.88, 58.86, 61.50, 127.79, 172.12,

Stereoselectivity When large rings are constructed by RCM, UE-isomeric mixtures can result. Hence RCM-based macrocyclizations are best suited for the preparation of intermediates in which the C-C double bond formed by metathesis can be removed (by, e.g., hydrogenation or oxidation) at a later stage of the synthesis. When trienes with two diastereotopic C-C double bonds are subjected to RCM, two diastereomeric dienes can be formed. Few examples of such reactions have been reported [886,887]. Interestingly, the stereochemical outcome of such cyclizations can be controlled by the choice of the catalyst (Entries 8 and 9, Table 3.19). Kinetic resolution of chiral dienes has been realized by RCM with enantiomerically pure molybdenum carbene complexes [888- 8901. High enantiomeric excesses of recovered diene (> 99% ee) and cycloalkene (93% ee) could be obtained.

156


Synthesis of Heterocycles

Table 3.19 lists examples of the preparation of nitrogen-containing heterocycles by RCM. As mentioned in Section 3.2.5.3, free amines can partly deactivate metathesis catalysts. With the highly reactive molybdenum catalyst 1 it is, however, possible to cyclize dienes containing a basic amino group. If the less reactive catalysts 2 or 3 are to be used, protonation or acylation of the amine can be used to reduce their nucleophilicity. This will generally lead to higher yields with smaller amounts of cata1y st. The examples in Table 3.19 show that RCM is a versatile tool for the preparation of lactams. This methodology is increasingly being used for the synthesis of natural products or analogs thereof [891-8931. In most of the reported examples N,N-disubstituted amides were used as starting materials, because the most stable conformer ( E ) of amides such as RCONHR can not undergo a cyclization reaction. As amides tend to have high C(0)-N bond rotation barriers, cyclization reactions generally proceed more readily with N,N-disubstituted amides (see e.g. [8931). However, as Entries 5 and 13 in Table 3.19 demonstrate, N-monosubstituted amides can also cyclize upon treatment with a metathesis catalyst. Particularly noteworthy examples are Entries 8 and 9 in Table 3.19; these represent a diastereoselective RCM in which the stereoselectivity is controlled by the catalyst [886]. Entries 17, 23 and 24 (Table 3.19) illustrate the use of RCM for the solid-phase synthesis of lactams [894]. RCM induces both ring closure to the lactam and cleavage from the support. Although elegant at first glance, the usefulness of this methodology will be limited if the products must be used without further purification (as is usually the case for compound libraries prepared by parallel synthesis). Because relatively large amounts of catalyst are required, the crude products will only be acceptable for assays in which transition metal complexes do not interfere. Table 3.20 lists examples of the preparation of oxygen-containing heterocycles by RCM. Further examples, including lactones [895], pyrans [896,897], chromenes [839l, tetrahydrofurans [838], phosphonates [898], and oxepines [856,899-9021, have been reported. For references to macrocyclizations see ‘Scope and Limitations’ in this section.


Table 3.19. Formation of nitrogen-containing heterocycles by ring-closing metathesis. Substrate

Conditions

Product

4% 1, 20 "c, C6H6,3 h

1

4% 2,20 "c, CH,Cl,, 36 h; then NaOH

p h L N a

5% 3, 20 "c, CH,CI,, 2 d

BOC-N

4% 3, 20 "c, C,H,, 32 h

Yield

Ref.

85%

[903]

79%

[813]

97%

[814]

Boc9 95%

[904]

76%

[905]

77%

[903]

66%

[906]

HO

HO

4% 1,20 OC, C6H6, 1.5 h

Ph

50% 2, 50 "C, C,H,, 24 h

F3kP 61%

[887]

97%

[887]

TBSO 0

TBSO

cisitrans 8:92

10% 1,80 "C, Cf,H6,3 d 0 TBSO

TBSO cisltrans

86: 14

157

158

3 Non-Heteroatom-SubstitutedCurbene Complexes

Table 3.19. continued. Substrate

Conditions

Product

1% 2,80 "C, C,H,, 40 min

Yield

Ref.

86%

[907]

70%

[908]

TsN+OAC

3% 2, 110 "c, PhMe, 48 h

BnO

ph-Ns

12

13

10% 2,20 "C, C,H,, 60 h TrO

14

/ J

5% 2,20 "C, C,H,, 72 h

86%

[903]

95%

[905]

93%

[909]

49%

[905]

91%

[910]

0

15

10% 2, C,H,, 20 "C, 1 d, 75 "C, 13 d

o

e

16

C0,Me

17

5% 3.20 "C. CH,CI,, 16 h; Ar: 2,4-dinitrophenyl

I

Oso"'" 62%

[911]

88%

[907]

3.2 Synthetic Applications of Non-Heteroatom-SubstitutedCarbene Complexes Table 3.19. continued.

w>

Yield

Ref.

10% 3,40OC, CH,CI,, 3 h

100%

(9121

4% 1,20"C, CdL 1h

73%

[903]

5%C&,2,20 92"C, h

73%

[909]

84%

[910]

16%

[911)

77%

[907]

87%

[914] ~921

Substrate

Conditions

TBSO

19

Product TBSO

0

20

Phv

21

c & 0

0

0

BocHN

POI

24

d' I

COzMe

5%3,80"C, 16h, 1,2-dichloroethane Ph

100% 3,50"C, PhMe, 16 h

Dog

0 Pol

1% 2,80 "C, C6H6,2.5h

C0,Me

4% 3,20 "C, CH,CI,, 5 h 0

159

I60

3 Nnn-Heteroutom-Substituted Curbene Complexes


Conditions

Product

Yield

Ref.

Ts

10% 3 , 4 0 "C, CH,CI,, 3 h 0

28

70% [912] 0

Fx

m

9% C6H6,4h 1,20 "C,

0

50%

[910]

0

MeOC , -,

MeozCl 10% 2,60"C, 29

x2

24 h

51%

[883]

78%

[910]

74%

[844]

I

g; BOG

30

15% 1,50 "C,

C&, 4 h

I

F,COd

COCF,

1% 1,40 "C,

CO,, 72 h; [Conc. (diene) 3 mM]

\

ZiE 29171

3.2 Synthetic Applicutions ( f Non-Heteroutom-SubstitutedCurbelie Complexes

161

Ally1 1-phenyl-3-butenyl ether (94 mg, 0.50 mmol) is added to a homogeneous, orange-red solution of the ruthenium complex 2 (9.3 mg, 0.01 mmol, 2%) in dry benzene (CAUTION!, 15 mL) under argon. The progress of the reaction is followed by TLC. After stirring for 5 h at 20 "C the reaction is quenched by exposure to air (until greenish-black; 6 h) and concentrated. The residue is purified by column chromatography (gradient elution with etherkexane 0: 1 to 6:94). 69 mg (86%) of the title compound is obtained as a colorless oil. (Note: A similar result will probably be obtained if the lengthy quenching procedure is omitted.)

3.2.5.7 Cross Metathesis The treatment of equivalent amounts of two different alkenes with a metathesis catalyst generally leads to the formation of complex product mixtures [925,926]. There are, however, several ways in which cross metathesis can be rendered synthetically useful. One example of an industrial application of cross metathesis is the 'ethenolysis' of internal alkenes. In this process cyclic or linear olefins are treated with ethylene at 50 bar/20480 "C in the presence of a heterogeneous metathesis catalyst. The reverse reaction of ADMET/RCM occurs, and terminal alkenes are obtained. Much more challenging is the targetted introduction of carbon substituents at terminal olefins by means of cross metathesis. Because of the mild reaction conditions under which alkene metathesis proceeds, cross metathesis could become an extremely valuable tool for the synthetic chemist if the critical parameters for productive cross metathesis between different, functionalized olefins were understood. The examples listed in Table 3.21 illustrate the synthetic possibilities of cross metathesis. In many of the procedures reported, advantage is taken of the fact that some alkenes (e.g. acrylonitrile, styrenes) undergo slow self metathesis only. Interestingly, it is also possible to realize cross metathesis between alkenes and alkynes (Table 3.21, Entries 11-13), both in solution and on solid supports [927,928]. Experimental Procedure 3.2.9. Cross Metathesis with a Molybdenum Catalyst in Homogeneous Phase: (E)-1-Phenyl-1-octene [929]

A \y +B 1

(CF,),MeCO-t!!to (CF,),MeCd

Ph

+ /

J - hP

Ph104.16

765.54

112.22

188.32

28.05

162


Table 3.20. Formation of oxygen-containing heterocycles by ring-closing metathesis. Substrate

Conditions

Yield Ref.

Product

RPh A

A+

93% [915]

Ph

13% 1,60 "C, hexane, 2 h

87% [871]

92% [916]

1% 2,40 "C, CO,, 12 h

1 %

\

8 (.,. SiMe,

e3

68% [917] 0

O 7CCI,

3% 3,20 'C, PhMe BnO

62% [844]

0

CCI,

93% [918]

.

OBn

13% I, 20 "C, pentane, 3.5 h I

Ph

A0

aPh 84% [871]

Ph

I

/o""

5% 3, 20 OC, CH,CI,, 16 h

43% [911] QPh

Pol

5% 2, ethylene, 22 OC, CH,CI,, 24 h (> 99% ee)

81% (> 99% ee)

[919] [9201

3.2 Synthetic Applications of Non-Heteroutom-Substituted Curbene Complexes


10

Conditions

-0

y0YPh 10% 3 , 2 5 "C, CH,CI,, 4 h

II

Product

Yield Ref.

coyph &

87% [813]

0

95% [921]

H

8% 2 , 5 5 "C, C& 2 h; (only 20% yield for cis-diastereomer)

12

13

10% 3 , 2 5 "C, CH,CI,, 4 h

60% [883]

e(J

95% [%I]

ti

Ph

14

3-6% 3 , 4 0 "C, CH,CI,, 3 h

I

I

-Si

30% 3,25-60 "C, C6H6, 2 d; [conc. (diene) 5 mM]

15

16 A

c

o

~

~

85% [922] W.31

][I! 45% %

5-7% 3 , 4 0 "C, , CH,CI,, Ih

89% [924] AcO

AcO

(f 10% dimer)

10% 2 , 7 0 "C, PhMe, 60 h, high dilution

86% [845]

163

164


Table 3.21. Preparation of alkenes and dienes by cross metathesis. Starting Components (Ratio)

H e x 4

Conditions

Product (Yield)

HexT TNo2 1% 1,20 "C, CH2CI2, 1 h

/

P

[929]

/

(48%;

(33:67) Hex

Ref.

+ 39% 7-tetradecene) C

(33:67)

N

5% 1,20 "C, Et,O, 10 h

(75%; Z/E 90:10) 5% 1,20 "C, fco2Bn @CN

v(33:67)

CN

CH,CI,, 3 h (44%; ZlE85:15;

+ 6% hornodirner of ester) 2% 1,20 "C, DME, 4 h

p h L s i M e 3

P311

(80%; ZIE 19:81)

(33:67) 5% I , 40 "C, CH,CI,, 12 h

P

oqT (74%; ZIE 3 1 :69)

(33 :67)

P

O

3% I , 40 "C, CH,CI,, 4 h (4456)

[933]

O

C0,Me

C0,Me

(66%; ZIE 33:67)

5% 1,40 "C, CH,CI,, 2 h (33:67) 5% I, 40 "C, CH,CI,, 16 h

(40:60) (98%)

165


Table 3.21. continued. Starting Components (Ratio)

Conditions

Product (Yield)

Ref.

10% 1,40 OC, CH,CI,, 8 h Me,Si (77%; 92% ee)

(97% ee; 40:60)

C0,Me

CO,Me

10% 3,20 "C, DCE, 30 h

P341 BocHN -ph

(33:67)

(52%; + 40% homodimer of ester) 7% 3, 20 "c, CH,CI,, 24 h

(25:75)

l2

(90"/; ZIE 25:75)

p\7

1% 3,20 "C, CH,CI,, 24 h

OBn

(25:75)

(82%; ZiE 5050)

0

3% 3,CH,CI,, ethylene, 45 20 h "C, l3

~

O

A

~

o

A

P361 c

C

(74%)

The molybdenum complex 1 (342 mg, 0.45 mmol, 1%) is added to a mixture of dichloromethane (90 mL), 1-octene (5.0 g, 44.6 mmol) and styrene (9.29 g, 89.2 mmol). The resulting mixture is stirred at room temperature for 1 h and then filtered through a pad of silica gel. After rinsing with dichloromethane the combined filtrates are concentrated and the crude product is purified by column chromatography (silica gel). 7.9 g (94%) of the title compound is obtained as a colorless oil. All the metathesis reactions discussed in this section require only catalytic amounts of a carbene complex. The use of stoichiometric quantities of carbene complexes in organic synthesis is limited to cheap metals such as, e.g., titanium.

166


Table 3.22. Examples of the preparation of dienes by ring-opening cross metathesis, Starting Components (Ratio)

Conditions

Product (Yield)

Ref.

5% 1 , 2 0 "C, CH,CI,, 3 h

(40:60)

R;b HB:

0

0

( 1 7:83)

5% 3 , 2 0 "C, CH2C12,24 h

:go "."'LAr

Wl

OMe

[61%, Ar: 4-MeOC6H,]

8%3 , 2 0 "C, CH2C12,3 h

0

(l0:90)

5% 3 , 2 0 "C, CH,CI,, 3.5 h

I.! ..,,(y

SiMe3 I...

&-NBoc 0

(50:SO)

(83%; ZIE 33:67)

7% 3, 20 "c, CH,CI,, 16 h HO

OH

'OH

(40:60)

(58%; ZIE 67:33)

10% 3 , 2 0 "C, CH,C12, 18 h Pol

(+ regioisomer; 5050; Ar: 3-chlorophenyl)

[938]

167

3.2 Synthetic Applications of Non-Heteroatom-SubstitutedCarbene Complexes Table 3.22. continued. Starting Components (Ratio)

Conditions

Product (Yield)

5% 3,20 "C, CH,CI,, 20 h

97% ee [1092]) can be achieved, it can be inferred that in the transition state of these C-H insertions the catalyst is in close proximity to the reacting groups. With the same type of catalyst highly enantioselective (up to 93% ee) intermolecular C-H insertions can also be realized [1093].

4.2.2.3 Intramolecular 1,2-C-H Insertions In acceptor-substituted carbene complexes with hydrogen at Cp. fast hydride migration to the carbene will usually occur [1094,1095]. The resulting olefins are often formed with high stereoselectivity. 1,2-Hydride migration will also occur in P-hydroxy carbene complexes, ketones being formed in high yields (Table 4.2). Intramolecular 1,5-C-H insertion can sometimes compete efficiently with 1,2-insertion [ 10961.

4.2 Synthetic Applications of Acceptor-Substituted Carbene Complexes

18 1

Table 4.2. Intramolecular 1,2-C-H insertion of acceptor-substituted carbene complexes. Starting Material

Reagents, Conditions -78 "C, 1% Rh2(02CCF3)4, CH,Cl2, 1 h

Product

-78 "C, 1% Rh2(02CCF3)4, CH2C12, 1 h

OMe

5% Rh,(OAc),, 20 "C, C,H,,

16h

NZ

Ref.

94% [lo971

C02Me

-78 O C , 1% Rh2(02CCF3)4, CH,C12, 1 h

N2

m+

7

Ph

Yield

80% [lo971

Hi5c72 92% [I0971

R

78% [I0981

0.5% Rh,(OAc).+,

20 "C, CH,CI,, lh

Ph&Ph BocNH

57% [974]

N,

4.2.2.4 Intramolecular 1,3-C-H Insertions Few examples of the formation of cyclopropanes by intramolecular C-H insertion of electrophilic carbene complexes have been reported. This methodology for cyclopropane preparation seems only to be suitable for polycyclic compounds with little conformational flexibility. Illustrative examples are listed in Table 4.3.

4.2.2.5 Intramolecular 1,4-C-H Insertions Intramolecular carbene C-H insertion is a suitable method for the preparation of four-membered carbo- or heterocycles. In particular p-lactams [ 1088,1101110.51 are formed easily, and often in high yields, upon transition metal-mediated diazodecomposition of N-alkyldiazoacetamides. 1,2-Azaphosphetidines [I 1061 also can be prepared by intramolecular C-H insertion into nitrogen-bound methylene groups. Few examples of the preparation of p-lactones by intramolecular C-H insertion have been reported [ 1107,1108]. This might be because of the ease with which p-lactones undergo ring-opening reactions or decarboxylation [ 1 1091. Examples of the formation of four-membered rings by intramolecular C-H insertion of electrophilic carbene complexes are listed in Table 4.4.

182

4 Acceptor-Substituted Carbene Complexes

Table 4.3. Intramolecular 1,3-C-H insertion reactions of electrophilic carbene complexes. Starting Material

1


Product

copper bronze, cyclohexene

Yield

Ref.

94% [lo991

N2

cuso,, 1 10 "C, 2

68% [IIOO]

PhMe, high dilution 0

4.2.2.6 Intramolecular 1,5-C-H Insertions Intramolecular carbene C-H insertion frequently leads to the formation of fivemembered rings [967,990,1021,1113- 11281. In particular 1-diazo-2-alkanones tend to yield cyclopentanones exclusively when treated with rhodium(I1) carboxylates. The use of enantiomerically pure catalysts for diazodecomposition enables the preparation of non-racemic cyclopentane derivatives [ 1005,1052,1074,1092,1129]. Intramolecular 1,5-C-H insertion can efficiently compete with 1,2-C-H insertion

4.2 Synthetic Applications o j Acceptor-Substituted Carbene Complexes

183

Table 4.4. Intramolecular 1,4-C-H insertions of electrophilic carbene complexes generated from diazocarbonyl compounds. Starting Material


Product

Yield

Ref.

53%

[IIIO]

0

I Yo Rh,(OAc),, 80 "C, C6H6,4 h PMP C0,tBu

(mixture of diastereomers)

1% Rh,(OAc),, 40 "C, CH,CI,, 20 h

Ph/YCOZEt

C0,Me 0

1% Rh,(OAc),, 40 "C, CH2CI2, 4h

O+N2

40 "C, CH2CI,, 2?h

CNXN2 Go

67% [ 1 1 1 1 ]

(97% ee)

(E: C0,Me)

K

Eto2C

N2

Co2Et

0.5% Rh,(OAc),, 20 "C, CH,CI,, 1.5 h

[1096,1116,1124], as illustrated, e.g., by the examples in Table 4.5 (Entries 13 and 14). Wolff rearrangement of the transient acylcarbene complex can, however, sometimes compete with intramolecular C-H insertion [ 1 1301. Although diazoacetamides are usually converted into p-lactams upon diazodecomposition, with some substrates pyrrolidinones can be the main product (Table 4.6) [ 1101,1102,1140,1141]. For instance, 1-diazoacetyl-2-ethylpyrrolidineyields, upon treatment with rhodium(I1) complexes only 1-methyl-3-pyrrolizidinone (i.e.

184

4 Acceptor-Substituted Curhene Complexes

Table 4.5. Preparation of cyclopentanones by intramolecular carbene 13-C-H insertion. Starting Material

G2


Product

I%Rh,(OAc),,

0 (80% de)

1% Rh,(OAc),, 40 "C, C,H,

-20 "C, CHZCI,,

2% PhtN

+N2Ph

Ph

x:

0 I/

I/

0

(98% ee) 0

NHPh "Ph 0

20 "C, CH,CI,,

3h AcO

N3"',~&N2

AcO

1% Rh,(cap),, 20 "C, CH,CI,,

5h OMe

OMe

Yield

Ref.

185

4.2 Synthetic Applications of Acceptor-Substituted Curbene Complexes Table 4.5. continued. Starting Material


Product

Yield

Ref.

I 3% Rh,(OAc),, 20 "C, CH,CI,

9

eN2

+

PO(OEt),

lo

61% [I1351 Ph

11

5% Rh,(OAc),, CH,CI,, 12 h

Rh2(0Ac)4

-$

PO(OEt),

85%

[I1361

62%

[I911

2% Rh,(OAc),, CH,CI,, 6 h

70% [I1371

Rh,(OAc),,

53% [I1381

0

6"

C0,Me

12

rn

C0,Me

l3

14

40 "C, CH,CI,

20 O C , 0.05% rhodium(l1) octanoate, CH,CI,, 10 min 20 "C, 0.01% rhodium(I1) octanoate, CH,CI,, 5 min

91% [I1391 p h (>~ 90% " cde)o ~ M e

-CO,Me

89% [I1391

186


Table 4.6. Preparation of pyrrolidines and pyrroles by intramolecular carbene 13-C-H insertion. Starting Material


Product

Yield

Ref.

CH,CI,, 2%

htNx'Bu Me0,C Ph$N-Ar .+'

(Ar: 4-nitrophenyl)

qPh 2

P/'P/

80% [I 1451

(74% ee)

,Th7yh 2% Rh,(OAc),,

98% [I1461

BryNxo N, C0,Et 20 "C, CHZCI,,

30 min Br

C0,Et

3

I Ph

N,

20 QC,2% Rh2(02CC3F7)4, CH,CI,, 2 h; then TIPSOTf, NEt,

C0,Et

53% [I1431

&OTIPS \

Ph

PhAN&

4

C0,Et

I

N,

Ph

I

20 "C, 2% fi,(HNCOCF3),, CH,CI,, 10 min; then TIPSOTf, NEt3

C0,Et

94% [I0801

p J $ s o T (l L P h

moTBS HN2 0

S0,Ph

5% rhodium(I1) octanoate, 80 "C, 0 C&,3 h 1

53% [I1471

S0,Ph TBS

0

20 "C, 2% Rh,('LS-MEPY), (see Fig. 4.20), CH,CI,, 20 h

C0,Me

a5

72% [I1161

(racemic)

1% Rh,(OAc),, 40 "C, CH,CI,, 4h

88%

[IIlO]


1 87

the product of 1,5-C-H insertion) [ 11421. Non-racemic pyrrolidinones can be obtained with enantiomerically pure rhodium(I1) complexes as catalysts [ 1088,11011. Further carbene precursors, which readily lead to the formation of five-membered rings upon diazodecomposition, are diazoacetanilides (Table 4.6) [ 1080,1110,1143]. With these substrates insertion into an aromatic C-H bond to yield 2-indolinones is often the predominant reaction pathway. The regioselectivity can however strongly depend on the type of catalyst and on the structure of the substrate (compare, e.g., Entry 4 in Table 4.6 with Experimental Procedure 4.2.1) [1143]. Diazoacetanilides also cyclize to 2-indolinones upon catalysis by acids [ 1 1441. ecu1)-3-

NO2

382.38

ide is prepared by N-arylation of L-phenylalanine 4-fluoronitrobenzene, 110OC, 10 h, ioxin-4-one, toluene, 110 "C, ethylamine, acetonitrile, 20 "C, 1.5 h, 90%).

phenyl)-N-(2-diazo-3-oxobutyryl)-L-pheny1alanine 01) in 1,2-dichloroethane (45 mL) is added over f rhodium(I1) acetate (48 mg, 0.11 mmol, 2.6%) in f,2-dichloroethane (30 mL) by means of a syringe motor. Concentration yields with a small amount of hot methanol. Recrystallization eptane yields 1.05 g (65%) of the title compound as mp 200-202 OC, [a],20-278 " (c 1.0, chloroform). on of a sample from heptane/e etate yields colorless plates, .53 (s, 3H), 3.41 (dd, 10.7, C. 'H NMR (200 MHz, CDC ,3.63 (dd, 5.1, 14.2 Hz, lH), 3. 3H), 5.34 (dd, 5.1, 10.7 Hz, lH), 6.88 (d, 8.8 Hz, lH), 6.99-7.19 (m, 5H), 8.08 (dd, 2.2, 8.8 Hz, IH), 8.20 (d, 2.2 Hz, 1H). Several examples have been reported for furanone formation by intramolecular C-H insertion of electrophilic carbene complexes [ 1006,11481 (Table 4.7). Yields can, however, be low with some substrates, possibly as a result of several potential side-reactions. Oxonium ylide formation and hydride abstraction, in particular, [ 1090,1149- 11521 (see Section 4.2.9) seem to compete efficiently with the formation of some types of furanones.

I 88

4 Acceptor-S~b,~titlrted Curbene Complexes

Table 4.7. Preparation of five-membered, oxygen-containing heterocycles by intramolecular carbene 1,5-C-H insertion. Starting Material


Qf

1 BnO ""

Product

80 1%"C, Rh,(OAc),, C,H,, 4 h

Yield

Ref.

62% [1107]

$0

BnO""

OTBS

OTBS 0

3

"3-

,,gc02Me

R

0.06% rhodium(I1) octanoate, 20 "C, CH,CI,,

wYo2Me 0

20 min

BnOi (R: geranyl)

58%

[I1201

BnOi (+ 32% C-3 diastereomer)

CHZCIZ, 0.5%

Bno/\Yoyo 04Q-E I/ I/

BnO

N2

/Yh7Yh

[ 11541

BnO' (86% de, 94% ee)

0L > E

a0

I/

(98% de, 97% ee)

(E: C0,Me) CH2CIz,0.5%

70% [I1551

Ac,

0

B ~ o " * ' ' ' ~65%~

I/

H

CHZCI,, 0.5% 6

0

A>E

0

I/

m

o

I/

(98% ee)

82% [lo071

I 89

4.2 Synthetic Applications of Acceptor-Substituted Carbenr Complexes Table 4.7. continued. Starting Material


Product

Yield

0

Ref.

67% [1156]

(94% ee)

0

1% rhodium(I1)

50%

[I0691

C&,, 4 h n

4.2.2.7 Intramolecular 1,6- and 1,7-C-H Insertions The formation of six-membered or larger rings by intramolecular C-H bond insertion normally requires the attacked position to be especially activated towards electrophilic attack [ 1 157,11581. Electron-rich arenes or heteroarenes [ 1159- 11621 and donor-substituted methylene groups can react intramolecularly with electrophilic carbene complexes to yield six- or seven-membered rings. Representative examples are given in Table 4.8.

4.2.2.8 Intermolecular C-H Insertions Few examples of preparatively useful intermolecular C-H insertions of electrophilic carbene complexes have been reported. Because of the high reactivity of complexes capable of inserting into C-H bonds, the intermolecular reaction is limited to simple substrates (Table 4.9). From the results reported to date it seems that cycloalkanes and electron-rich heteroaromatics are suitable substrates for intermolecular alkylation by carbene complexes [ 11651. The examples in Table 4.9 show that intermolecular C-H insertion enables highly convergent syntheses. Elaborate structures can be constructed in a single step from readily available starting materials. Enantioselective, intermolecular C-H insertions with simple cycloalkenes can be realized with up to 93% ee by use of enantiomerically pure rhodium(I1) carboxylates [ 10931.

190

4 Acceptor-Substituted Curbene Complexes

Table 4.8. Preparation of six- and seven-membered carbo- and heterocycles by intramolecular carbene C-H insertion. Starting Material


Product

Yield

Ref.

(78% ee) OMe

IPh

1 eq. CuCI, -45 "C, CH,CI,, 3h

90% [I0171 Me0

83% [ I 1631

3% Rh,(OAc),, 80 "C, C6H,, 2.5 h CF3

& AN2

82% [I1641

0

1.1 eq. DMAD,

60% [I1331

Rh,(OAc),, 25 "C, C,H,, 1 h

0 Ph

Ph

co+!N2 1% Rh2(cap),, 40 "C, CH,CI,, 10h

O

y

2

L O T , ,

67% [I1531

H

1% Rh,(OAc),, 20 "C, CH,CI,, lOh

80% [lo901 (two diastereomers50:50)

4.2 Synthetic Applicutions of Acceptor-Substituted Carbene Complexes

Table 4.9. Intermolecular C-H insertion reactions of electrophilic carbene complexes. Starting Material


Product

Yield

Ref.

62%

[993]

R

I

1 H

H

N2

10% Rhz(OAc),, 120 oc, 6 h, pinacolone

1% Rh2(OAc),, 4 eq. thiophene,

20 OC, PhF, 15 h

H

H

(R:3,4-dirnethoxybenzyl)

b?

94% [I1661

OH

% qPh 0

3

\\

1% Rh2(OAc),, 25 "C, THF, 0.5 h

73% [lo711

Ph

C0,Me

Ph

4

"K

0

co2Me

N2

83% [lo931

(81% ee)

//

5

0

N P C O , ~ B U

//

5% Rh,(OAc),,

20 "C, CH2C12, 18h

85% C0,tBu

I11671

191

192


Experimental Procedure 4. Insertion: 3-(lli-3-1ndolyl)-

U ~ X C-H

12b.09

4.2.3 Si-H Insertions Silanes can react with acceptor-substituted carbene complexes to yield products resulting from Si-H bond insertion [695,1168-11711. This reaction has not, however, been extensively used in organic synthesis. Transition metal-catalyzed decomposition of the 2-diazo-2-phenylacetic ester of pantolactone (3-hydroxy-4,4dimethyltetrahydro-2-furanone) in the presence of dimethyl(pheny1)silane leads to the a-silylester with 80% de (67% yield; [991]). Similarly, vinyldiazoacetic esters of pantolactone react with silanes in the presence of rhodium(I1) acetate to yield a-silylesters with up to 70% de [956].


193

4.2.4 C-C Insertions Carbenes do not usually undergo intermolecular C-C bond insertions [1172]. Intramolecular 1,2-insertions into C-C bonds are, however, frequently observed [976], and have, e.g., been used for the synthesis of strained bridgehead olefins [ 1 1731. Further examples are listed in Table 4.10. Table 4.10. 1,2-C-C Insertion of electrophilic carbene complexes. Starting Material

1 OH


Product

oy&

0.5% 20 "C, Rh,(OAc),, CH,Cl,, lh

Yield

Ref.

57%

[974]

NZ

0.2% Rh,(OAc),, 60 "C, hexane,

2

80% [ I 1741

1.5 h; then SiO,

C0,k

3

OH

73% [1175]

20 "C, CHCI,, 5 rnin

NZ

H

0.5% Rh,(OAc),,

C0,Et

4% U d O A c h , 20 "C, pentane, 30 rnin

0,

tBu0

4.2.5

C0,Et

90%

[977]

tBU0

X-H Insertions (X: N, 0, S)

Electrophilic carbene complexes can react with amines, alcohols or thiols to yield the products of a formal X-H bond insertion (X: N, 0, S). Unlike the insertion of carbene complexes into aliphatic C-H bonds, insertion into X-H bonds can proceed via intermediate formation of ylides (Figure 4.7).

194


yZ ML,

+

RNX'H (X = N, 0,S )

ML"

2 - 2

Y -

RXX'H

RNX

Fig. 4.7. Possible mechanism of the X-H bond insertion of electrophilic carbene complexes.

Ylide formation, and hence X-H bond insertion, generally proceeds faster than C-H bond insertion or cyclopropanation [ 11761. 1,2-C-H insertion can, however, compete efficiently with X-H bond insertion 111771. One problem occasionally encountered in transition metal-catalyzed X-H bond insertion is the deactivation of the (electrophilic) catalyst L,M by the substrate RXH. The formation of the intermediate carbene complex requires nucleophilic addition of a carbene precursor (e.g. a diazocarbonyl compound) to the complex L,M. Other nucleophiles present in the reaction mixture can compete efficiently with the carbene precursor, or even lead to stable, catalytically inactive adducts L,M-XR. For this reason carbene X-H bond insertion with substrates which might form a stable complex with the catalyst (e.g. amines, imidazole derivatives, thiols) often require larger amounts of catalyst and high reaction temperatures. 4.2.5.1

N-H Insertions

The first reports of N-H insertion reactions of electrophilic carbene complexes date back to 1952 14971, when it was found that aniline can be N-alkylated by diazoacetophenone upon treatment of both reactants with copper. A further early report is the attempt of Nicoud and Kagan [ 11781 to prepare enantiomerically pure a-amino acids by copper(1) cyanide-catalyzed decomposition of a-diazoesters in the presence of chiral benzylamines. Low enantiomeric excesses (< 26% ee) were obtained, however. Because of partial deactivation of many catalysts by aliphatic amines, less nucleophilic derivatives such as carboxamides or carbamates are usually used as substrates for carbene N-H insertion. The usefulness of this reaction for the preparation of heterocycles under mild conditions became apparent in 1978, when chemists from Merck, Sharp & Dohme reported the synthesis of bicyclic p-lactams by intramolecular carbene N-H insertion 11 1791. Intramolecular N-alkylation of p-lactams by carbene complexes is one of the best methods for preparation of this important class of antibiotic and many p-lactam derivatives have been prepared using this methodology [ 1180 -11861 (Table 4.11). Intramolecular N-H insertion can also be used to alkylate amines [1187-11891, y-lactams [1190], and carbamates [1191-11931 (Table 4.11). Intermolecular N-H insertion of electrophilic carbene complexes has occasionally been used for the preparation of amino acid derivatives and other types of intermediates (Table 4.12) 1956,1043,1194- 12011.


195

Table 4.11. Preparation of nitrogen-containing heterocycles by intramolecular N-H insertion of electrophilic carbene complexes. Starting Material

Reagents, Conditions 0.5% Rh,(OAc),, 1% NEt,, 0 "C, CH,CI,, 14 h

Ph+Nz

1

Product

Ref.

63% (12021

"--)-'-fO ,NJ

WN2

Boc

BocNH

2

Yield

C0,PNB

0. I%Rh,(OAc),,

100% 112031

0

80 OC, PhMe 0 -

C0,PNB

0

OMe

O h C02Bn

GyNZ

0

5% Rh,(OAc),, 80 "C, C6H6,

25 rnin

X

O

57% [1204]

0

C02Bn

%&

0

1% Rh,(OAc),, 20 "C, C,H,, 1 h

50% [1205] 0

C0,PNB

OPNB

0.3% Rh,(OAc),, 20 "C, CHCI,, 2 h

0

94% [1188] Et0,C

R

=

TBSO

TBSO

4

~

F,C

80 "C, 5% Rh2(02CCF3)4, DCE, 10 h

o a o c

C02Bn

0.3% 20 OC, Rh,(OAc),, CH,CI,

"

77% 110571

n

C02R2 0 I\

V

(R': PhOCH,CONH; R2: 4-nitrobenzyl)

O

H

87% [I0511

CO,RZ

Ph

0

C0,Me

1% Rh,(OAc),, 80 "C, C6H6,

C0,Bn

30 rnin

8 N2

HN,

Rh,(OAch, 80 'C, C,H6

9

75% [1206] 0

"'(F$,H

50% [1207]

tBu0,C 0

'0

196

4 Acceptc~r-Substituteu'Curbene Complexes

Table 4.12. Intermolecular N-H insertions of electrophilic carbene complexes. Starting Material


Product

Yield

Ref.

I10 "C, 5 eq.

1

EtOzCyPO(OEt), NZ

VNm= H 2% Rh,(OAc),,

46% [1198] I

Boc

PhMe, 15 h 2

EtOzCKPO(OEt),

4-nitroaniline, 110 "C, 5 eq. N2

3

K cozMe

Ph

NZ

o z N ~ N ~ ( o E t 81% ) z

2%Rh2(OAc),,

PhMe, 15 h

H

[1198]

C0,Et

PhYozMe

110 "C, 1 eq.

67% [I1971

diethy lamine,

vNo

2% Rh2(OAc),, PhMe, 12 h

OEt

PhMe, 14 h

OEt

4.2.5.2 0 - H Insertions The reaction of acceptor-substituted carbene complexes with alcohols to yield ethers is a valuable alternative to other etherification reactions [ 1152,1209- 121 11. This reaction generally proceeds faster than cyclopropanation [ 11761. As in other transformations with electrophilic carbene complexes, the reaction conditions are mild and well-suited to base- or acid-sensitive substrates [1212]. As an illustrative example, Experimental Procedure 4.2.4 describes the carbene-mediated etherification of a serine derivative. This type of substrate is very difficult to etherify under basic conditions (e.g. NaH, alkyl halide [ 1213]), because of an intramolecular hydrogen-bond between the nitrogen-bound hydrogen and the hydroxy group. Further, upon treatment with bases serine ethers readily eliminate alkoxide to give acrylates. With the aid of electrophilic carbene complexes, however, acceptable yields of 0-alkylated serine derivatives can be obtained.

4.2 Synthetic Applications of A~cept(~r-Substitute~ Carbene Complexes

197

Experimental Procedure 4.2.4. Etherification of a Serine Derivative by Intermolecular 0-H Insertion: Methyl (2S)-3-[(Ethoxycarbonyl)methoxy]-2-(benzyloxycarbony1amino)propanoate Zaragoza, F., Ullmann, A., unpublished results

Ho/yCo*Me (

“ZEt

+

HN\CO,Bn

N*

2S3.26

114.10

441.99

-“X

C0,Me

Rh,(OAc),

Eto2C

C0,Bn

339.3s

A solution of ethyl diazoacetate (1.33 g, 11.7 mmol, 2.9 eq.) in dichloromethane (20 mL) is added over 18 h to a refluxing mixture of N-Cbz-serine methyl ester (1.02 g, 4.03 mmol), dichloromethane (10 mL), and rhodium(I1) acetate (42 mg, 0.095 mmol, 2.4%). The resulting mixture is concentrated under reduced pressure and the residue is purified by column chromatography (60 g silica gel, gradient elution with heptanelethyl acetate 9:l to 6:4). 0.85 g (62%) of the title compound is obtained as a colorless oil. ‘H NMR (200 MHz, CDCl,) 6 1.22 (t, 7 Hz, 3H), 3.72 (m, 4H), 4.01 (m, 3H), 4.16 (q, 7 Hz, 2H), 4.45 (m, lH), 5.09 (s, 2H), 6.01 (d, br, 7 Hz, lH), 7.23 (m, 5H); I3C NMR (50 MHz, CDCl,) 6 14.01, 52.51, 54.25, 60.97, 66.82, 68.18, 71.17, 127.83, 127.96, 128.33, 136.24, 156.00, 169.95, 170.38. A broad range of compounds can be 0-alkylated with carbene complexes, including primary, secondary, and tertiary alcohols, phenols, enols, hemiaminals, hydroxylamines, carboxylic acids, dialkyl phosphates, etc. When either strongly acidic substrates [ 12141 and/or sensitive carbene precursors are used (e.g. aliphatic diazoalkanes [ 12151 or diazoketones) etherification can occur spontaneously without the need for any catalyst, or upon catalysis by Lewis acids [1216]. Enantiomericaliy pure phenyldiazoacetic esters [ 12171 and vinyldiazoacetic esters [956] react with alcohols upon transition metal catalysis to yield aalkoxyesters with low diastereoselectivity (< 53% de). Intramolecular 0-H insertion enables the preparation of 3-%membered cyclic ethers in high yield [979,1193,1218- 12201. Examples of 0-H insertion reactions are given in Tables 4.13 and 4.14. One side-reaction occasionally observed in carbene complex-mediated etherifications is the oxidation of the substrate by hydride abstraction (see Section 4.2.9).

4.2.5.3 S-H Insertions S-Alkylation of thiols by carbene complexes can be a useful approach to a-(alky1thio)- or a-(arylthio)ketones, although few examples of intramolecular [975,1193] or intermolecular [497,1043,1230- 12331 S-H bond insertion reactions of electrophilic carbene complexes have been reported. Yields are sometimes low, probably because of the poisoning of the catalyst by the thiol. Examples are given in Table 4.15.

198


Table 4.13. Preparation of cyclic ethers by intramolecular 0-H insertion of electrophilic carbene complexes. Starting Material

1

P

h N3


Yield

Ref.

&(OAc)4

90% [1221]

1Yo Rh,(OAc),, 80 "C, C6H6

92% [I2221

q C02Et N2

C02tBu

2

Product

*


4

H 0 a c 0 2 k

13% Rh,(OAc),, 20 "C, CH,CI,, 48 h

C0,Et

3% Rh,(OAc),, 80 "C, C,H6, 40 min

C0,Me

C?Tco4.2.6

1% Rh,(OAc),, 1 10 "C, PhMe,

90%

[lo801

53% [I2231

77% [I2241

16h

Ylide Formation

Acceptor-substituted carbene complexes are electrophilic intermediates which react readily with lone pairs, giving the corresponding ylides. These can be valuable intermediates, capable of undergoing a broad range of synthetically useful transformations. This subject has been treated in several reviews [38,995,1077- 1079,10861.

4.2.6.1 Ammonium Ylides Tertiary amines can react with electrophilic carbene complexes to yield ammonium ylides which usually undergo Stevens rearrangement (Figure 4.8) leading to products of a formal carbene C-N bond insertion.


199

Table 4.14. Preparation of ethers by intermolecular 0-H insertion of electrophilic carbene complexes. Starting Material


Product

Yield

Ref.

66%

[993]

80 "C, C,H,, 1 eq. 1

J

C0,Me NZ

1Yo Rh,(OAc),, 20 min

0

72% [I2251

2

/ \

tBu

CH,CI,, 6 h; (E: C0,Et)

/ \

tBu

tBu

tBu

40 "C, 2 eq.

1% Rh,(OAc),, CH,CI2, 1.5 h tevt- butanol,

4

Rh2(0Ac)4, 130 "C, 1.5 h 2 eq. catechol, 1% Rh2(OAc),, 80 "C, C,H,, 15h

(EtO),OPKCOZMe

5 NZ


"6' 42% [1227]

(E1O),OPyCO,Me

83% [1201] HO

6

7

Rh2(0Ac)4, EtozC-fCozEt 84% [I2281 EtozC-TfCo2Et ethanol 0NZ

r.4

) ,N

Nz

8% 2-propanol, Rh,(OAC),, cNLo'( 20"C, CH,Cl,, ) ,N H 20 h; then TFA

40% [1229]

200


Table 4.15. Preparation of thioethers by S-alkylation of thiols with electrophilic carbene complexes. Starting Material


Product

Yield

Ref.

41%

[975]

2%Rh,(OAc),,

80 "c, C&, 5 min

2

2% Rh2(OAc),,

3

C0,Et

80 " c , C6H6, 1.5 h

C0,Et

73% [1193]

N2

Fig. 4.8. Formation and Stevens rearrangement of ammonium ylides from acceptorsubstituted carbene complexes.

Allylammonium ylides can undergo 2,3-sigmatropic rearrangement [ 12341. With weakly nucleophilic amines, C-H bond insertion or hydride abstraction can compete efficiently with ammonium ylide formation. Intramolecular N-alkylation of tertiary amines, followed by Stevens rearrangement, enables rapid preparation of elaborate polycyclic structures [ 1235- 12381. Illustrative examples are given in Table 4.16.

186.17


20 1

Table 4.16. Generation and rearrangement of ammonium ylides from diazocarbonyl compounds and tertiary amines. Starting Material


Product

Yield

Ref.

84%

[I0181

Bn02C

5% Cu(acac),, 1 10 "C, PhMe

& (900/, de)

/N

fxN2 3% Rh,(OAc),, 20 "C, CH,Cl,

99% [1135]

ph*

5% Cu(acac),, 110 "C, PhMe, 1.5 h

86% [I2391 Ph

0

62% [I2401

2% Cu(acac),, 80 "C, C,H,

3% Rh,(OAC),+, 80 "C, DCE, 10 h

& j

52%

[954]

C02Me Ph CNJPh

K

F3c

N2

\ 65% [I1991

202


4.2.6.2 Azomethine Ylides The intermolecular reaction of imines with acceptor-substituted carbene complexes generally leads to the formation of azomethine ylides. These can undergo several types of transformation, such as ring closure to aziridines [ 1242- 12451, 1,3-dipoIar cycloadditions [ 1 133,1243,1246- 12481, or different types of rearrangement (Figure 4.9).

Fig. 4.9. Formation and transformations of azomethine ylides from imines and electrophilic carbene complexes.

The scope of these reactions has not yet been thoroughly investigated. The examples listed in Table 4.17 suggest that azomethine ylides generated by intramolecular, carbene-mediated N-alkylation of imines enable convergent and fast

4.2 Synthetic Applications o j Acceptor-Substituted Carhene Complexes

203

preparations of polycyclic heterocycles. Entry 2 is particularly interesting because the azomethine ylide is only formed from the E-oxime. With the corresponding Z-oxime intramolecular C-H insertion into the vinylic C-H bond of the oxime occurs [ 11331. Table 4.17. Generation and rearrangement of azomethine ylides from acceptor-substituted carbene complexes and imines. Starting Material

1


Meo2CK co2Me N,

Product

llO°C, 1.2eq. PhCH=NMe, 1.2 eq. PhCHO, Rh2(0Ac)4, PhMe. 3 h

Ref.

68% [1133]

Ph

Ph

2.7 eq. DMAD, Rh2(0Ac)4, 40 "C, CH2C12, 2.5 h N,

Yield

C0,Me

OMe

(R: OMe)

3 eq.DMAD, 0.1% Rh2(OAc),, 80 "c,C6H6, 12 h

Meo&

1.2 eq. DMAD, 0.3% Rh2(OAc),, 20 "C, CHCI,, 1 h

0

65%

[1249]

4.2.6.3 Nitrile Ylides The generation of electrophilic carbene complexes in the presence of nitriles or other cyano-group-containing compounds can lead to the formation of nitrile ylides. With acylcarbene complexes the final products are often 1,3-oxazoles [ 11941, presumably formed by the mechanism sketched in Figure 4.10.

204


Fig. 4.10. Possible mechanism for the formation of 1,3-oxazoles from acylcarbene complexes and nitriles.

Table 4.18. Preparation of 1,3-oxazoles from acceptor-substituted carbene complexes and nitriles. Starting Material


Product

Yield

Ref.

5% Rh,(OAc),,

98% [I2511

N,N-diethy Icyanamide (neat), 60 "C, 3 h O,N

1Yo Rh,(OAc),,

propionitrile, 25 "C, 3 h

&N2

0

2% Rh,(OAc),, chloroacetonitrile, 80 "C, 10 h OMe

K

Meo2c Co2Me N2

I % Rh,(OAc),, 0.1 eq. PhCN, 68 "C, CHCI,, 29 h

Ph

Trapping of the intermediate acyl nitrile ylide with dimethyl acetylenedicarboxylate leads to pyrroles in low yields (< 18%) [1250]. Representative examples of the preparation of oxazoles with carbene complexes are listed in Table 4.18.

4.2 Synthetic Applications qf Acceptor-Substituted Curbene Complexes

1

205

(R = CH,CHR,)

Fig. 4.11. Generation and transformations of oxonium ylides from electrophilic carbene complexes.

4.2.6.4 Oxonium Ylides Ethers can react with electrophilic carbene complexes to yield oxonium ylides, which usually undergo either elimination reactions or 1,2-alkyl shifts to yield products of a formal carbene C-0 bond insertion (Figure 4.1 1) [ 1020,1255- 12591. With allyl ethers highly diastereoselective, concerted 2,3-sigmatropic rearrangements are often observed [ 1260- 12641. An elegant application of such stereoselective rearrangements was reported by Pirrung in 1991 (Figure 4.12). Intramolecular 0-alkylation of an allyl ether followed by 2,3-sigmatropic rearrangement was the key step in the first total synthesis of (+)-griseofulvin, a natural fungicide. In this example the 2,3-sigmatropic rearrangement proceeded both with high diastereoand enantioselectivity (Figure 4.12). If chiral catalysts are used to generate the intermediate oxonium ylides, nonracemic C-0 bond insertion products can be obtained [ 1265,12661. Reactions of electrophilic carbene complexes with ethers can also lead to the formation of radical-derived products [ 1 135,12591, an observation consistent with a homolysisrecombination mechanism for 1,2-alkyl shifts. Carbene C-H insertion and hydride abstraction can efficiently compete with oxonium ylide formation. Unlike free carbenes [ 1267,12681 acceptor-substituted carbene complexes react intermolecularly with aliphatic ethers, mainly yielding products resulting from C-H insertion into the oxygen-bound methylene groups [ 107 1,10931. Examples of reactions which presumably involve oxonium ylides are listed in Table 4.19. Experimental Procedure 4.2.6. Oxonium Ylide Formation and 2,3-Sigmatropic Rearrangement: Ethyl 2,5-Dimethoxy-4-pentenoate [ 12641

102.13

114.10

189.23

206


-

C0,Me

6 steps

32%

Me0

D

MeO+O

Nz

62%

OMe

I

5% Rh,(piv), 80 'C, C,H,, 1 h

3. TFA 4. (PhO),P(O)N,

OMe

5. HCI, H,O D

MeO

56%

-

1, NaOMe, MeOH 2. CH,N,, THF

II

47%

'

0

0 Me0

P (+)-griseofulvin

(Pirrung, 1991)

Fig. 4.12. Synthesis of non-racemic griseofulvin based on intramolecular oxonium ylide formation [ 12621.

4.2.6.5

Carbonyl Ylides

When acceptor-substituted carbene complexes are generated in the presence of carbonyl compounds, carbonyl ylides can be formed. These intermediates can undergo a wide variety of further transformations [38,1079] (Figure 4.13). Treatment of aldehydes or ketones with acceptor-substituted carbene complexes leads to formation of enol ethers [1271- 12741, oxiranes [1048], or 1,3-dioxolanes [989,1275] by 0-alkylation of the carbonyl compound. Carboxylic acid derivatives

207


Table 4.19. C-0 Bond insertion reactions of acceptor-substituted carbene complexes generated from diazocarbonyl compounds. Starting Material

Reagents, Conditions N2CHC02Et,

MeO-SiMe,

Product

Yield

Sib,

68% [I2631

1Yo Rh2(OAc),,

25 "C, CH2CI2

pN* 0 -

Ref.

-YCOZO E tW (94% de)

CH,C12, 2% Cu(MeCN),PF,, 3% A[''

62% [I0141 (57% ee)

CH,CI,, 1% Cu(MeCN),PF,

QqL?

46% [I2601 OW

0 0

C0,Me

20 OC, hexane, 96% [I2691

\\ (60% ee)

95% [I1351

15% Cu(hfacac),, 40 "C, CH2C1,

86%

40 "C, CH,Cl,, 0

1%

[988]

cLa' (8lY0 ee)

can react with electrophilic carbene complexes to yield ketene acetals [ 1 102,1276 or oxiranes [ 12771. With diazocarbonyl compounds as carbene precursors cyclization of the initially formed carbonyl ylide to 1,3-dioxoles can ensue [ 1275,12791. Dihydrofurans can result either from a$-unsaturated carbonyl compounds and electrophilic carbene complexes [ 12801 or from carbonyl compounds and vinylcarbene complexes.

- 12781

208


Table 4.19. continued. Starting Material


Product

P

h

4

2% CuOTf, 20 "C, D["I

Ref.

31%

[I0301

Ph .

N ~ C O , ~ B ~

8

Yield

tBu0,C

0 0

(cisltrans 24:76\

A

B

C

D

Of great synthetic potential is the ability of carbonyl ylides to undergo interor intramolecular 1,3-dipolar cycloadditions to alkenes [ 1075,1281- 12971, alkynes [1287,1292,1293,1296- 12981, reactive ketones [1299], or acylnitriles [1297]. Asymmetric induction can be achieved with enantiomerically pure rhodium(I1) carboxylates as catalysts [ 13001. The synthetic possibilities of this process have been thoroughly investigated, in particular by the research group of A. Padwa. Elaborate polycylic structures can be prepared by intramolecular generation and cycloaddition of carbonyl ylides from simple starting materials (Figure 4.14). Some of these products have been used as intermediates for the synthesis of natural products. Some examples of transformations involving carbonyl ylides are listed in Table 4.20. Entry 1 illustrates the conversion of P-acyloxy-a-diazoesters into a-acyloxyacrylates by ring fission of a cyclic carbonyl ylide [978]. This reaction has been used for the synthesis of the natural aldonic acid KDO (3-deoxy-Dmanno-2-octulosonic acid), which is an essential component of the cell wall lipopolysaccharide of gram-negative bacteria (Figure 4.15).

209


f 0

(R = CHR,)

Z

?

R

W

h

4

R

/

1

HC=CR',)

R

Fig. 4.13. Formation and reactions of carbonyl ylides from carbonyl compounds and electrophilic carbene complexes.

cat. Rh,(OAc), 50 'C, C,H,

*

I

95% C0,Me

(Padwa, 1995)

Fig. 4.14. Preparation of polycyclic compounds by intramolecular 1,3-dipolar cycloaddition of carbonyl ylides to alkenes (13011.

2 10

4 Acceptor-Substituted Curbene Complexes 1. N,CHCO,Et (neat), 7 d (74%) 2. Ac,O, pyridine (100%)

1% Rh,(OAc), CHCI,

D

TBSO

HO

P

TBSO AcO

N,

100%

C0,Et

4.3. NH, AcOH , H,O 92%

OH

HO 4Hbc i , .

(Lbpez Herrera, 1997)

OH KDO

Fig. 4.15. Synthesis of KDO using ethyl diazoacetate as synthetic equivalent of the anion of glyoxylic acid ethyl ester [980].

2 11

4.2 Synthetic Applications of Acceptor-Substituted Curbene Complexes

Table 4.20. Generation and transformations of carbonyl ylides from electrophilic carbene complexes. Starting Material


bOSiMe, Co,Me

2

Rh,(OAc),, 70 "C, C,H,

Product

0

Yield

Ref.

66%

[1302]

70%

[992]

85%

[992]

COPe

@ ..OSiMe,

NZ

0

Ph I

3 Me0,C

Ph

80 "C, 0.2% Rh2(NHCOC3F,), Ph

I

'0'

4

Me0

Me0,C

Ph

80 "C, 0.2% Rh,(OAc),

Ph

(pol: polymeric support) PhCHO, dimethyl maleate, 4.4%

6 NZ

N

I

Rh2(02CC3F7)4, CH,CI,, 8 h

'N Z U

'I..

Me0,C

COzMe

C02Me

bU2CI

7 /

p,,Qsirn3

DMAD, 0.4 % Rh,(OAc),, 20 "C, C,H,, 0.5 h 0

49% [ 13041

2 12




Product

6 %Rhz(OAc),, 20 "C, CH,CI,, lh

Yield

Ref.

75% [I2711

H

45%

9

10

w~~ CH,CI,, 5 eq. 2-cyclohexenone, 0.1% rhodium(I1) octanoate

[I3051

62% [1271] (mixture of diastereomers)

The outcome of reactions involving carbonyl ylides is not always as easy to predict, as the examples in Table 4.20. Depending on the basicity of the intermediates, proton migrations might occur and unexpected results can be obtained. Two examples of such peculiar conversions and the proposed mechanisms are sketched in Figure 4.16.


\ N / ~ ~

2 13

0.2% Rh,(OAc), DMAD, 20 “C C,H, 10 min c

Meozca Me0,C

\AyPh

PkN/

60%

0

* o

Me0,C

C0,Me

(Padwa, 1996)

Fig. 4.16. Atypical reactions of carbonyl ylides generated from carbonyl compounds and acceptor-substituted carbene complexes [ 1276,13061.

4.2.6.6 Sulfonium Ylides If acceptor-substituted carbene complexes are generated in the presence of thioethers, ylide formation is generally the mostly favored process. The resulting sulfonium ylides are often sufficiently stable to be isolated [975,1307- 13091. Typical reactions of sulfonium ylides include 1,2-alkyl migration, leading to products of

2 14


a formal carbene C-S insertion reaction (Figure 4.17). This rearrangement proceeds particularly smoothly with ally1 thioethers through a concerted 2,3-sigmatropic rearrangement [975,1231,1234,1266,1310- 13131. If enantiomerically pure catalysts are used to generate the sulfonium ylide, the 2,3-sigmatropic rearrangement can take place with significant asymmetric induction [ 1314,13151. Thioacetals are also suitable substrates for carbene C-S insertion [ 1264,1309,13161. In reactions involving sulfonium ylides fewer side-reactions than with oxonium ylides are usually observed. This is probably because of the stabilization of the former by dx-pn interaction; this is not possible with oxonium ylides.

z R2

'R

R'

R'

Fig. 4.17. Generation and typical transformations of sulfonium ylides.

In addition to 1,2-alkyl shifts, sulfonium ylides with P-hydrogen can also undergo fragmentation into an olefin and a thioether [ 1317,13181. When allylic thioethers are treated with two equivalents of ethyl diazoacetate in the presence of a catalyst for diazodecomposition, S-alkylation and elimination of the thioalkyl group from the initially formed a-alkylthio-4-alkenoic esters occurs to yield 2,4-dienoic esters [1319]. Interestingly, sulfonium ylides generated from electrophilic carbene complexes and sulfides can react with carbonyl compounds, imines, or acceptor-substituted alkenes to yield oxiranes [ 1320- 132.51, aziridines [ 1321,1326,13271 or cyclopropanes [1328,1329], respectively. In all these transformations the thioether used to form the sulfonium ylide is regenerated and so, catalytic amounts of thioether can be sufficient for complete conversion of a given carbene precursor into the


of

2 15


Table 4.21. Reactions of thioethers with electrophilic carbene complexes. Starting Material

K

Meo2c co2Me

p


Product

Yield

Ref.

psph W0zk C0,Me

89% [I3091

0

N2

Rh2(0Ac)4, 40 "C, CH,CI,

SPh U

C02Me 0.5% Rh,(OAc),,

78% [I3111

80 "C, C6H6, 30 min

1% Rh,(OAc),,

77% [I3321

80 "C, C6H6, 30 min '

C0,Me

Rh6(c0),2

29% [lo111

(+ 6% other diastereomers)

1% Rh,(OAc),, 80 "C, C,H6

56% [I3161 H

0x0

0 x 0

2% Rh,(OAc),, 25 "C, CH,Cl,, 20 min

83% [I0711

2 16


Fig. 4.18. Possible mechanism of the olefination of thiocarbonyl compounds with electrophilic carbene complexes [ 13361.

corresponding three-membered, cyclic product. Enantiomerically pure thioethers have been used, in combination with a catalytically active copper or rhodium complex, to convert diazoalkanes into the corresponding, more nucleophilic, chiral sulfonium ylides. These can undergo the reactions sketched in Figure 4.17 in an enantioselective fashion [ 132I , 1323,1324,1326- 13281. The conversion of acceptor-substituted diazomethanes into carbene complexes often does not proceed smoothly in the presence of sulfides. This might be because of poisoning of the catalyst by the sulfide [975]. Higher yields of sulfonium ylides can, however, be obtained by HBF,-mediated reaction of acceptor-substituted diazomethanes with sulfides [lo1 1,1328,1330,1331]. Representative examples of reactions of acceptor-substituted carbene complexes with thioethers are given in Table 4.21.

4.2.6.7

Thiocarbonyl Ylides

When thiocarbonyl derivatives are treated with an excess of electrophilic carbene complex, alkenes are usually obtained [ 1333- 13361. The reaction is believed to proceed by the mechanism sketched in Figure 4.18, closely related to the thiocarbonyl olefination reaction developed by Eschenmoser [ 13371. Few examples have been reported in which stable thiiranes could be isolated [1338]. The intermediate thiocarbonyl ylides can also undergo reactions similar to those of carbonyl ylides, e.g. 1,3-dipolar cycloadditions or 1,3-oxathiole formation [ 13381. Illustrative examples of these reactions are given in Table 4.22. When planning reactions of thiocarbonyl compounds with electrophilic carbene complexes it should be taken into account that thiocarbonyl compounds can undergo uncatalyzed 1,3-dipolar cycloaddition with acceptor-substituted diazomethanes to yield 1,3,4-thiadiazoles. These can either be stable or eliminate nitrogen to yield thiiranes or other products similar to those resulting from thiocarbonyl ylides 113381.


of

2 17


Table 4.22. Reactions of thiocarbonyl compounds with acceptor-substituted carbene complexes. Starting Material


Product

Yield

Ref.

H

U

80 "C, C6H6,4 eq. N,CHCO,Et,

1

49% [1339]

0.4% Rh,(OAc),,

16h

S

CHC0,Et

MeO,d

C0,Me

tBu

4

CozMe N,

tBu

COzMe

66% [1342]

3% Rh,(OAc),, 80 "C, C6H6 tBu

4.2.6.8 Other Ylides Phosphonium ylides can be generated by treatment of diazoacetates and triphenylphosphine or triethyl phosphite with catalytic amounts of RuC12(PPh,), [ 13431 or ReOCl,(PPh,), [1344]. If these reactions are conducted in the presence of aldehydes, carbonyl olefination takes place in high yields. Electrophilic carbene complexes can also react with organic halides to yield halonium ylides. Reaction of acceptor-substituted carbene complexes with ally1

2 18


bromide, for instance, leads, via 2,3-sigmatropic rearrangement, to a formal insertion of the carbene into the C-Br bond [ 1231,12341. Diacylcarbene complexes can also abstract chloride from 1,2-dichloroethane, presumably by intermediate formation of a chloronium ylide [ 1 1661. Finally, stable cyclic iodonium ylides can be prepared by intramolecular iodine alkylation with electrophilic carbene complexes [ 1345,13461,

4.2.7 Cyclopropanation One of the most efficient procedures for the synthesis of cyclopropanes is the reaction of alkenes with electrophilic carbene complexes. In this process up to three stereogenic centers can be generated in one step. Cyclopropanes are a key structural element encountered in many natural products with interesting biological activity. Further, by virtue of the ability of cyclopropanes to undergo ring-opening reactions these compounds can be valuable synthetic intermediates. 4.2.7.1

Scope and Limitations

A wide range of olefins can be cyclopropanated with acceptor-substituted carbene complexes. These include acyclic or cyclic alkenes, styrenes [ 10151, 1,3-dienes [1002], vinyl iodides [ 1347,13481, arenes [1349], fullerenes [1350], heteroarenes, enol ethers or esters [ 1351- 13541, ketene acetals, and N-alkoxycarbonyl[ 1355,13561 or N-silyl enamines [ 13571. Electron-rich alkenes are usually cyclopropanated faster than electron-poor alkenes [626,10 151. Alkynes can be converted into cyclopropenes by inter- [587,1022,1052,106010621 or intramolecular [ 10701 cyclopropanation with electrophilic carbene complexes. Because of the high reactivity of cyclopropenes, however, in some of these reactions unexpected products can result from rearrangement or other transformations of the cyclopropenes initially formed (cf. Section 4.1.3). Alkenes with strongly electron-withdrawing groups or strained alkenes are generally not suitable substrates for cyclopropanation with electrophilic carbene complexes. These alkenes tend to undergo fast 1,3-dipolar cycloaddition with diazocarbonyl compounds (i.e. the carbene complex precursors) to yield 3Hpyrazolines. The latter can either be stable or rearrange to IH-pyrazolines. In some cases 3H-pyrazolines eliminate nitrogen upon thermolysis or photolysis to yield the corresponding cyclopropanes [ 13501. The most thoroughly investigated carbene precursors for inter- or intramolecular cyclopropanations are diazoacetic acid derivatives. Cyclopropanations with vinyldiazoacetic esters have been investigated in detail by the group of H. M. L. Davies. The products resulting from the cyclopropanation of arenes often undergo electrocyclic rearrangement to cycloheptatrienes (Figure 4.6) [ 1358- 13601. Treatment of donor-substituted alkenes with acylcarbene complexes can lead to the formation of donor-acceptor-substituted cyclopropanes which can readily undergo ring fission and/or rearrangement to dihydrofurans. Reactions of this type will be discussed in Section 4.2.8.


2 19

4.2.7.2 Stereoselectivity Experimental results [ 13611 and theoretical treatment [28] indicate that the cyclopropanation of alkenes by electrophilic carbene complexes is a concerted process. Z-Olefins normally lead to the formation of the corresponding cis-cyclopropanes, and E-olefins yield truns-cyclopropanes. The relative configuration of the carbenebound substituent and the substituents of the alkene in the final cyclopropane seems to be mainly determined by the steric bulk of these groups. In cyclopropanations of terminal alkenes with ethyl diazoacetate low diastereoselectivities are often observed [ 1024,135 I]. These can be improved by increasing the steric demand of the substituents at the carbene or at the alkene [ 1033,13621. High diastereoselectivities can, e.g., often be achieved with tert-butyl, neopentyl or 2,6-di(tert-butyl)phenyl diazoacetate [ 13621 as carbene complex precursors (Figure 4.19). 1% Rh,(acac), 10 eq. 1-hexene 20 “C, CH,CI,

-

N,

Bu\lrl/CozEt + (37: 63)

1% Rh,(acac), 10 eq. 1-hexene 20 OC, CH,CI, c

80%

N,

Bu&cozR

+ (7 : 93)

““‘4 C0,Et

““‘4 CO,R

(Doyle, 1990)

Fig. 4.19. Enhancement of diastereoselectivity in intermolecular cyclopropanations with sterically demanding diazoacetates [ 13621.

The catalyst can also have a significant influence on the stereoselectivity of cyclopropanation reactions [ 10231. For instance, cyclopropanation of styrene with ethyl diazoacetate and copper or rhodium catalysts normally proceeds with low diastereoselectivity. With ruthenium porphyrines as catalysts, however, up to 92% de can be achieved [1041,1042]. The inter- or intramolecular cyclopropanation of achiral alkenes with enantiomerically pure diazoacetic esters [ 1016,1363,13641 or amides [ 1365,13661 does not usually proceed with high diastereoselectivity. A chiral auxiliary which occasionally gives good results is pantolactone (3-hydroxy-4,4-dimethyltetrahydro-2-furanone) [ 1016,1367,1368]. The most elegant strategy for the preparation of enantiomerically enriched cyclopropanes is based on the use of chiral catalysts (for recent reviews, see [ 1072-

220


1

2

Ph

r( Ph

3

Rh,(SS-MEPY),

Rh,(SS-MPPIM),

Fig. 4.20. Complexes for asymmetric cyclopropanation with acceptor-substituted diazomethanes. 1 [1372], 2 [ 13731, 3 [ 10331, Rh,(SS-MEPY),, Rh2(5S-MPPIM), [1001,1074]. For related rhodium-based catalysts, see, e.g., [997,1000,1002].

10741). Since the first experiments with chiral copper complexes reported by Nozaki [650] and Aratani [ 10271 many different catalysts have been examined, both for intermolecular and intramolecular cyclopropanations (for a review, see [ 13691). Syntheses of natural products [955,1370] and drugs [ 13711 using asymmetric cyclopropanation with chiral electrophilic carbene complexes have been reported. A selection of useful catalysts is given in Figure 4.20 (see also Experimental Procedure 4.1.1). For intermolecular cyclopropanations with unsubstituted diazoacetates the highest asymmetric inductions can be achieved with the copper(1) complexes of C,-symmetric, bidentate ligands developed by Pfaltz (e.g. 1) and Evans (2). The chiral rhodium(I1) complexes known today do not generally lead to such high enantiomeric excesses as copper complexes in intermolecular cyclopropanations. For intramolecular cyclopropanations, however, chiral rhodium(l1) complexes are usually superior to enantiomerically pure copper complexes [ 13741.

4.2.7.3 Intramolecular Cyclopropanations Intramolecular cyclopropanation with acceptor-substituted carbene complexes is a powerful method for the synthesis of bicyclo[n. l.O]alkanes [ 1359,137513781. Several different ring sizes can be prepared, including macrocycles [ 1359, 13791 (Table 4.23). Intramolecular cyclopropanation has often been used for


catalys_t

0

O

Ph

D

+

22 1

+

Ph 4

catalyst: Rh,(O,CC,F,), catalyst: Rh,(cap),

catalyst: Rh,(cap),

(100 : 0)

(72% yield)

catalyst

catalyst: Rh,(O,CC,F,),

(0 : 100)

(95% yield)

a

&

+

(0 : 100)

(56% yield)

(100 : 0)

(76% yield)

Fig. 4.21. Chemoselectivity of different rhodium(I1) carbene complexes [990,1082].

the synthesis [ 1016,1050,1349,1380- 13841 or modification [ 10531 of natural products or analogs thereof [ 1385,13861. Several chiral complexes have been tested for their ability to control the stereochemical outcome of intramolecular cyclopropanations. High enantioselectivities have been attained using enantiomerically pure copper complexes [ 1387,13881 and rhodium complexes [ 1000,1001,1006,1049,115I , 1348,1374,1387,1389- 13921. Intramolecular C-H bond insertion and ylide formation can compete with cyclopropanation. As shown in Figure 4.21, however, the chemoselectivity of the intermediate carbene complex can sometimes be controlled by the remaining metal-bound ligands [21,990,1075,1081,12231. Experimental Procedure 4.2.8. Enantioselective, Intramolecular Cyclopropanation: 6,6-Dirnethyl-3-oxabicyclo[3.1 .O]hexan-2-one [ 13901

~~~~1- $: C0,Me

.(

[Rh,(6R-MEPY) J

154.17

916.55

126.16

ution of 3-methyl-2-butenyl diazoacetate (14.9g, 96.7 m o l ) in dichloromethane (450 mL) is added over 30h to a refluxing solution of Rh,(SR-

222


Table 4.23. Intramolecular cyclopropanation by transition metal-catalyzed decomposition of diazocarbonyl compounds. Starting Material


Product

Yield

Ref.

tgu

N2

TBSO

4

f 0

OM

100% [1393]

(Ar:3,5-tBu2-4-MeC,H2) cyclopentadiene, 1% Rh2(OAc),, 40 "C, CH2C12, 3h

S0,Ph

OTBS

a

S0,Ph

98% [1393]

OTBS

PO(OMe),

20 "C. 4% Q r & h

4%Rh2(OAc),, 20 "C, CHCIj, 10 min

C0,Me

C0,Et

91% [lo121

75% [I1751

2% Rh2(OAc),, 40 "C, CH,C12, 3h

77% [1394]

N,

N, 0

I

3% Rh,(OAc),, 0 "C, CH2C12, 3 min

87% [I3951

PMB

(+ C-2 epimer; 87:13) C0,Et

-78 "C, 1% Rh2(02CCF3)4, CH2C12,1 h

-a

EtOZC..

H

86% [lo971


223

Table 4.23. continued. ~~

Starting Material


Product

Yield

Ref.

h

8

2)

PhS

9

0

5% Pd(OAc),,

20 "C, C,H, [Rh,(OAc), leads to sulfonium ylide formation]

Ph

3% Rh,(OAc),, 10

80 OC, DCE, 9 h

12

63% [1310]

q;J 0

61% [I0831

C0,Me

[I3961

(74% de)

(Ar:2-tolyl)

I1

@r"h H

1% Rh,(OAc),, 20 "C, CH,CI,, 5h

Q

CH,CI,, 1 .O% Cu(MeCN),PF,, 1.2%

82% [I3971

(90% ee) tdu

teU

61% [I3541

224


4.2.7.4 Intermolecular Cyclopropanations The preparation of cyclopropanes by intermolecular cyclopropanation with acceptor-substituted carbene complexes is one of the most important C-C-bond-forming reactions. Several reviews [995,1072- 1074,1076,1077,1081]and monographs have appeared. In recent decades chemists have focused on stereoselective intermolecular cyclopropanations, and several useful catalyst have been developed for this purpose. Complexes which catalyze intermolecular cyclopropanations with high enantioselectivity include copper complexes [ 1025,1026,1028,1029,1031,1373,1398- 14001, cobalt complexes [ 1033- 10351, ruthenium porphyrin complexes [ 1041,1042,1230], C,-symmetric ruthenium complexes [948,1044,1045], and different types of rhodium complexes [955,998,999,1002- 1004,1010,1062,1353,1401 - 14051. Particularly efficient catalysts for intermolecular cyclopropanation are C,-symmetric copper(1) complexes, as those shown in Figure 4.20. These complexes enable the formation of enantiomerically enriched cyclopropanes with enantiomeric excesses greater than 99%. Illustrative examples of intermolecular cyclopropanations are listed in Table 4.24. Experimental Procedure 4.2.9. tion: Ethyl (1S)-2,2-Dimethyl-l

ermole

clopropana-

CuOTf,

212.61

A +f

cozEt

J2

56.11

114.10

A solution of the chiral ligand (67 mg, 0. is added to a suspension of copper(1) tri

c

2(

C0,Et

142.20


of Acceptor-Substituted Carbene

Complexes

225

Table 4.24. Intermolecular cyclopropanation by transition metal-catalyzed decomposition of diazocarbonyl compounds. Starting Material


C0,Me

Product

Yield

Ref.

N,CHCO,Et, 2.4% Rh,(OAc),, 20 "C, CH,CI,, 12h

dN-C02Bn

H

(cislfrans38:62) Boc I

Boc

N,CHCO,Me, 0.2% Cu(OTf),, PhN,H,, CH,CI,

0

45% [1407] C0,Me H

9

OTBS

?TBS

TBSO

3 eq. N,CHCO,Et, 2% Rh,(OAc),, CH,CI,, 10 min

C0,Et

85% [1408]

TBSO OTBS

OTBS

25 "C, 10 eq. EtOCH=CH,, 1% Rh,(OAc),,

CH,CI,

q+"

93% [I0661

Ph

OEt

1-butene, 1%

Ar's05? Ph

T

Ph

o"

f N2

\\

00

' 0

I/

I/

/Yh7Yh

(> 95% ee)

(AK4-tBuC,H,)

25 OC, pentane

oeE C0,Me

20 "C, CH,CI,, 1% N2kco2Me>

+

OEt

I

E

I/

I/

10 equivalents

t

O

p

OEt

(> 98% ee)

(E: C0,Me)

42% [lo601

226


Fig. 4.22. Formation of 1,3-dipoles by ring fission of donor-acceptor-substituted cyclopropanes.

4.2.8 Formal 1,3-Dipolar Cycloadditions of Acyl- and Vinylcarbene Complexes The reaction of heteroatom-substituted alkenes with electrophilic carbene complexes can lead to the formation of highly reactive, donor-acceptor-substituted cyclopropanes. This type of cyclopropane usually undergoes ring fission and rearrangement reactions under milder conditions than do unsubstituted cyclopropanes (Figure 4.22). For this reason unstable cyclopropanes or only rearrangement products are obtained when donor-substituted alkenes react with acceptor-substituted carbene complexes [1409- 14161. In reactions of acyl- and vinylcarbene complexes with enol ethers the most common types of rearrangement observed are those shown in Figure 4.23. In particular the synthetic approach to dihydrofurans (first equation in Figure 4.23) represents a useful alternative to other syntheses of these valuable intermediates, and has been used for the preparation of substituted pyrroles [1417], aflatoxin derivatives [ 14181, and other natural products [ 14191. The reaction of vinylcarbene complexes with dienes can lead to the formation of cycloheptadienes by a formal 13 + 41 cycloaddition [1367] (Entries 9-12, Table 4.25). High asymmetric induction (up to 98% ee; [1420]) can be attained using enantiomerically pure rhodium(I1) carboxylates as catalysts. This observation suggests the reaction to proceed via divinylcyclopropanes, which undergo (concerted) Cope rearrangement to yield cycloheptadienes. Rearrangement of non-donor-substituted vinylcyclopropanes can be induced by transition metals [ 1421- 14231 or thermally [ 1424- 14271. The thermal isomerization, however, requires high reaction temperatures (typically 200-500 "C).

4.2 Synthetic Applications cf Acceptor-Substituted Curbene Complexes

227

Fig. 4.23. Rearrangement of donor-substituted acyl- and vinylcyclopropanes.

Experimental Procedure 4.2.10. Cycloaddition of an Acylcarbene Complex to an Enol Ether: Ethyl 5-Ethoxy-2-trifluoromethyl-4,5-dihydro-3-furoate [14171

210.11

72.11

254.21

A mixture of ethyl 2-diazo-4,4,4-trifluoro-3-oxobutyrate(58.5 g, 0.28 mol), hydroquinone (100 mg), rhodium(I1) acetate (100 mg, 0.23 mmol, 0.08%), and ethyl vinyl ether (500 mL) is heated to 100°C for 8 h in a closed steel vessel (CAUTION!). The mixture is concentrated under reduced pressure and the residue purified by column chromatography (silica gel, ethyl acetateheptane 4:l). 65g (91%) of the title compound is obtained as an oil. lH NMR (100 MHz, CDC1,) 6 1.25 (t, 3H), 1.29 (t, 3H), 3.10 (m, 2H), 3.75 (m, 2H), 4.20 (9, 2H), 5.68 (dd, 3.0, 7.5 Hz, 1H).

Experimental Procedure 4.2.1 1. Cycloaddition of an Acylcarbene Complex to an Alkyne: Ethyl 2-Methyl-5-phenyl-3-furoate [ 143I]

156.14

102.14

230.27

228

4 Acceptor-Substituted Carhene Complexes

Table 4.25. Formal 1,3-dipolar cycloaddition of acyl- and vinylcarbene complexes to alkenes, alkynes, and dienes. Starting Material


p yo & 0

Product

Yield

Ref.

rhodium(I1) octanoate, CH,CI, 0

1Yo Rh,(OAc),, furan, PhF, 20 "C, 15 h

92% [I1661

1% Rh,(OAc),, N-acetylindole, PhF, 20 "C, 15 h

62% [1166]

2% Rh,(OAc),, 2 eq. triacetyl glucal, 20 "C, PhF, 10 h

34% [1166]

Ho"d~co

HO

65% [I4281

Rh,(OAc),, PhF

O

L-

0

3% rhodium(I1) octanoate, 80 "C, C,H,, 30 min

78% [I0671 \

Ph

229



Product

3%rhodium(II) mandelate, 80 "C, C&,3 h

I

cyclopentadiene; Rh2(0Ac)4,

9

6


Yield

Ref.

72% [I0691

A

E t o 2 c ~ C O z E t 80% [I2281

EtozCYKCo2Et then 110 "C, PhMe, 12 h

Tom:;{;2:, OTBS 0

10

&lTBS

63% [I4291

(R: Boc)

Boc'

OTBS 0

l 1 +o>

N*

NI Boc

1% rhodium(I1) octanoate, 69 "C, hexane, 1 h

53% [I4291

230


1

Z

L

(X = 0, NR)

0-

1% rhodium(l1) octanoate 69 OC,hexane, 1 h C

Boc'

ooT

-

Boc'

0

-------c

O

49%0

\

O

S

/S

BOG'"

1

(Davies, 1996)

Fig. 4.24. Reaction of electrophilic carbene complexes with furans and pyrroles leading to ring-opening of the heterocycle [ 14291.

4.2 Synthetic Applicutions of Acceptor-Substituted Carbene Complexes

23 1

4.2.9 Ring Fission of Pyrroles and Furans The reaction of acceptor-substituted carbene complexes with pyrroles and furans can lead to surprising results. Derivatives of these heterocycles are often attacked by electrophilic carbene complexes at C-2. The resulting intermediates can either tautomerize to give the products of carbene C-H insertion, or undergo ring-opening of the heterocycle to yield a$-unsaturated carbonyl compounds [ 1162,1367,14321 or imines (Figure 4.24). These can either be isolable, or undergo further transformations. Examples of such reactions are given in Figure 4.24 and in Table 4.26. Table 4.26. Ring fission of furans and pyrroles by acceptor-substituted carbene complexes. Starting Material


_c-i;

Product

Yield

Ref.

20 "C, 1.75 eq. 2-hexy lfuran,

58% [I4331

1% Rh,(OAc),,

Et02C

C02Et

rhodium(I1) octanoate, CH,CI,

E

t

O

q

P

O

rhodium(I1) octanoate, CH,C1,

1% rhodium(I1) octanoate, 69 O C , hexane, 1 h Boc

60%

[987]

75%

[987]

77% [I4291

232


4.2.10 Other Synthetic Applications of Acceptor-Substituted Carbene Complexes The normal byproducts formed during the transition metal-catalyzed decomposition of diazoalkanes are 'carbene dimers' and azines [496,1023,1329]. These products result from the reaction of carbene complexes with the carbene precursor. Their formation can be suppressed by slow addition (e.g. with a syringe motor) of a dilute solution of the diazo compound to the mixture of substrate and catalyst. Carbene dimerization can, however, also be a synthetically useful process. If, e.g., diazoacetone is treated with 0.1% RuCICp(PPh,), at 65 "C in toluene, cis-3-hexene2,5-dione is obtained in 81% yield with high stereoselectivity [1038]. A further, often observed, side-reaction is the oxidation of a given substrate by the carbene complex via hydride abstraction [1083,1084,1090,1118,1149-11521. Examples of such oxidations are shown in Figures 4.5 and 4.25. No catalysts or carbene precursors have, however, yet been reported, which lead to preparatively useful amounts of oxidized product.

1% Rh,(OAc), 20 OC, CH,CI,

0

oL +

I

OBn

58%

37% (Lee, 1995)

s I

Fig. 4.25. Hydride abstraction by acceptor-substituted carbene complexes [ 1090,11491.

5 Bibliography

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2 3 4 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 30 31 32 33 34 35 36

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86 81

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98 99 100 101

I02 103 104 105 106 107

108 109 110 111 112 1 I3 I I4 1 I5 116 1 I7

I I8 119 120 121 122 123 124 125

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236 I26 I27 128 129 130 131 132 133 I34 I35

136 137 138 139 140 141 142 143 144 145 I46 147 148 I49 150 151

I52 1.53 154 155

156 157

I58 159 I60 161 162 163 164

16.5

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252 822 823 824 825 826 827 828 829 830 83 1 832 833 834 835 836 837 838 839 840 84 I 842 843 844 845 846 847 848 849 850 85 1

852 853 854 855 856 857 858 859 860 86 I 862 863 864

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5 Bihliogruphy 865 866 867 868 869 870 87 1 872 873 874 875 876 877 878 879 880 88 I 882 883 884 885 886 887 888 889 890 891 892 893 894 895 896 897 898 899 900 901 902 903 904 905 906 907 908 909 910 91 1 912

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254 914 915 916 917 918 919 920 92 1 922 923 924 925 926 927 928 929 930 93 1 932 933 934 935 936 937 938 939 940 94 I 942 943 944 945 946 947 948 949 950

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1351 1352 1353 1354

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Index

76,77 84, 87, 89, 101 - electrophilic 29-3 1, 77, 82-90 - of halides 31, 89, 110 - of hydride 29-31, 83, 109, 122, 179, 197, 232 - nucleophilic 76-82 - of oxygen-bound leaving groups 84-87, 108, 110, 111 - of pyridine 45 - of thioethers 87, 106, 109, 111, 123, 124 Acceptor-substituted alkenes - cyclopropanation 45, 47-49, 11 1, 115, 117, 120, 218 - 1,3-dipolar cycloadditions to 115, 118, 211, 212, 218 - as Michael acceptors 68 - olefin metathesis 8, 150, 151, 157-159, 164 - preparation 180, 181, 232 Acceptor-substituted diazomethanes - C-acylation/alkylation 173, 210 - as carbene complexe precursors 171232 - as cocatalysts for olefin metathesis 140 - preparation 172 - stability 173 Acetals, reaction with carbene complexes 205-208 Acetylenes - see Alkynes Acidity, of heteroatom-substituted carbene complexes 35 Acrolein dimethylacetal 206 Acrylates - see Acceptor-substituted alkenes Abstraction

Acry lonitrile

- conjugate

- cross metathesis

161, 164, 166 cycloaddition to isonitrile complexes 22 C-H Activation - see C-H Insertion Acyclic diene metathesis (ADMET) 137, 148, 149, 161 Acyl complexes - 0-alkylation/O-acylation 14-20, 85, 86 - from carbonyl complexes 14, 19, 20 - conversion to vinylidene complexes 86 - from metallates 14, 18, 19 - photolysis 33, 34 Acyl halides 15 - reaction - with acyl complexes 14, 15 - with diazo compounds 173 - with metallates 18, 19 - with titanium carbene complexes 125 Acylcarbene complexes - see Acceptor-substituted carbene complexes ADMET - see Acyclic diene metathesis Aflatoxin 226 Alcohols - as cocatalysts for olefin metathesis 139 - etherification 196-199 - reaction with alkoxycarbene complexes 35, 68 - reaction with ketene complexes 41, 43, 68, 72 Aldehydes - 0-alkylation 206, 211 - condensation with heteroatom-substituted carbene complexes 35, 36 -

268

Index

condensation with isonitrile complexes 21, 22 - conversion to oxiranes 214 - [2 + 21 cycloaddition of 41 - in olefin metathesis 141, 144, 152 125, 126, 128, 130 - olefination - reaction with diazoalkanes 173, 210 - reaction with metallates 85 Aldol additions 35 Alkanes - alkylation of 179-192 - elimination of 78-82 - metallation 119-121 Alkene metathesis - see Olefin metathesis Alkenes - from carbonyl compounds 125-134 - from diazo compounds 116, 180, I8 1 , 232 - isomerization 137, 143, 144, 150 see also [2 + 21 Cycloadditions, Cyclopropanation, etc. Alkenyl complexes, reaction with electrophiles 98 Alkenylcarbene complexes - see Vinylcarbene complexes a-Alkoxyalkyl complexes 84-86 Alkoxycarbene complexes - see Heteroatom-substituted carbene complexes Alkoxynaphthols 50 Alkoxyphenols 49 Alkyl complexes - from carbene complexes I 19, 121 p-elimination 37, 38, 57, 63, 84 Alkyl halides - reaction with nucleophilic complexes 20, 29, 35, 87-89, 91, 95, 97, 99 - reaction with acylcarbene complexes 217 Alkyl nitrites 172 Alkyl triflates 15, 16 Alkylaluminum halides - see Organoaluminium compounds Alkyne complexes - intermediates in benzannulations 49 - isomerization to vinylidene complexes 25-27, 98, 101, 102 Alkynes - benzannulations with 49-55 -

- conversion to carbene complexes

2527, 98, 101, 102, 177 - cross metathesis with alkenes 161, 165 - cyclopropanation 110, 176, 177, 218, 225 46, 135-137, 148, 165 - metathesis - metathesis polymerization 135, 137, 141 - reaction with acylcarbene complexes 227-229 - reaction with alkoxycarbene complexes 42, 49-73 Alkynyl complexes, reaction with electrophiles 25, 29, 98 Alkynylcarbene complexes - cycloadditions to 36, 37, 54 - as dienophiles 36, 37, 54, 58, 60 - as Michael acceptors 36, 37, 56, 59, 61, 69 - preparation 19, 100 Allenes - cyclopropanation 108, 118 - preparation 131 Allyl amines, cyclopropanation 117, 225 Allyl ethers - 0-alkylation 205 - isomerization by carbene complexes 144 - RCM 153, 154, 156, 162, 163 Allyl halides 21 7, 2 18 Allyl silanes - cross metathesis with alkenes 164-167 - cross metathesis with alkynes 165 - preparation 152, 162, 164-167, 207 - ROMP 146 Allyl stannanes - cross metathesis 164 - preparation 164 Allyl thioethers - S-alkylation 214, 215 - cyclopropanation 223 - metathesis 143 Aluminium trichloride, as cocatalyst for olefin metathesis 75, 140 Amalgam, sodium 29, 30 Amides - see Carboxamides Amines 43, 45, - acylation by ketene complexes 63, 64

Index addition to alkynylcarbene complexes 36, 37, 69 - N-alkylation 194-1 96, 198, 200-202 - hydride abstraction 178, 179 - quaternization 198, 200-202 - RCM 157-160 - reaction with carbene complexes 35, 156 Amino acids - from chromium carbene complexes 41, 43 - cyclopropanation 117 - olefin metathesis 149, 158-160, 165 - norbornene derivatives, ROMP 147 Aminocarbene complexes - see Heteroatom-substituted carbene complexes 2-Amino- 1,3-dienes 58, 72, 73 Aminoindenes 49, 50 Aminophenols, by benzannulation 52, 53 Ammonium ylides - from acylcarbene complexes 198, 200-202 - from chromium ketene complexes 43, 45, 63, 64 Anhydrides - reaction with metallates 19 - reaction with titanium carbene complexes 126, 128 Aniline - as additive for olefin metathesis 140 - N-alkylation by acceptor-substituted carbene complexes 194, 196 - reaction with alkoxycarbene complexes 35 Arenes - acylation by ketene complexes 41 - alkylation by C-H insertion 180, 186, 187, 189-191 - cyclopropanation 180, 21 8, 223 - see also Benzannulation Aryl iodides, I-alkylation 21 8 Arylcarbene complexes - Experimental Procedure 91 - see also Non-heteroatom-substituted carbene complexes Asymmetric cyclopropanation - see Cyclopropanation, enantioselective 1-Aza- 1,3-dienes 72 -

269

Azepines C-alkylation 183 - by RCM 159 - from vinylcarbene complexes 71, 72 - Experimental Procedure 71 Azetidines - N-alkylation 64, 201 - preparation 230 Azetidinones - conversion to carbene complexes 24 - by N-H insertion 195 - see also P-Lactams Azides - 1,3-dipolar cycloaddition 32 - as reagents for diazogroup transfer 172 - transformation 184, 198 2-Azidopyridinium salts, diazogroup transfer with 172 Azines 25, 27, 232 Aziridines - from imines and carbene complexes 71, 202 - from imines and sulfonium ylides 214 - reaction with carbonyl complexes 18 - reaction with carbyne complexes 32 Azomethine ylides 64, 202, 203 -

Back-donation 2-5 Bamford-Stevens reaction 173 Benzannulation 41, 44, 49-55 - Experimental Procedures 52, 54 Benzofurans, preparation by RCM 162 Benzoquinones, from alkoxycarbene complexes 52-54 Bicyclo[n. 1 .O]alkanes 46-48, 107, 220223 Bicyclo[ 1.1.O]butanes - as carbene complex precursors 119 - preparation 119, 222 Block copolymers 141 Bond energies 3-5 - in tantalum carbene complexes 78 Boranes 35 Boron trichloride, as cocatalyst for olefin metathesis 141 Bromination, of carbyne complexes 99 1,3-Butadiene - see Dienes

270

Index

Calixarenes 149 Carbalkoxycarbenes - see Acceptor-substituted carbene complexes Carbamates - N-alkylation 194-196 - macrocyclic 149 Carbanions - see Organolithium compounds, Grignard reagents Carbazoles 44, 53, 55 - by benzannulation - by intermolecular C-H insertion 191 Carbene complexes, acceptor-substituted 171-232 - N-alkylation of amines 194-196 - 0-alkylation of alcohols 196-1 99 - S-alkylation of thiols 197, 200 - cyclopropanations with 2 18-226 - dimerization 116, 232 - generation 171-177 - C-C insertion 193 - C-H insertion 179-1 92 - Si-H insertion 192 - reaction with lone pairs 198-218 Carbene complexes, heteroatom-substituted - by a-abstraction 29-31 - acidity 35 - from acyl complexes 14-20 - from alkynes 25, 26 - analogy to carboxylic acid derivatives 35, 36 - from carbenoids or carbenes 27-29 - from carbonyl complexes 15-17 - from carboxamides 22-24 - from carbyne complexes 32, 33 - from 2-chloropyridinum salts 21 - demetallation 37-41 - from isonitrile complexes 21 - from metallates 18, 19 - as metathesis catalysts 140, 153 - by olefin metathesis 33, 34 - from organolithium compounds 15-17 - oxidation 37, 39, 40 - photolysis 33, 64 - by photolysis 33, 34 - preparation 14-34 - reaction - with alcohols 35, 36, 68 - with alkynes 42, 49-55, 67

- with carbon nucleophiles

38, 42, 68, 124 - with tin derivatives 38, 40, 42 - with ylides 38, 42, 91 - reduction 84 - reduction by dihydropyridines 45 - theoretical treatments 3-5, 13 - from thioureas 29 - use in organic synthesis 34-73 - from vinylidene complexes 25-27 Carbene complexes, non-heteroatomsubstituted - from alkenyl- and alkynyl complexes 98 - from alkynes and cyclopropenes 98-100 - carbonyl olefination with 125-135 - from carbyne complexes 93-98 - cyclopropanation with 6, 45, 71, 105-119 - by [2 + 21 cycloreversion 100 - by electrophilic abstraction 82-89 - by nucleophilic abstraction 78-82 - in olefin metathesis 6, 7, 134, 140-144 - preparation 45, 75-103 - Experimental Procedures 80, 86, 91, 95 - stability 75, 144 - theoretical treatments 3-5 - from ylides 90-93 Carbenes 1-3 - precursors for carbene complexes 27-29 - reaction with ethers 205 - stable 27-29 Carbocations 2, 122 Carbohydrates - metal-containing derivatives 16, 19, 26, 34 - metal-free derivatives 53, 210, 21.5, 225, 228 - norbornene derivatives, ROMP 147 - preparation of derivatives by RCM 158, 160, 162 Carbon dioxide, olefination 131 Carbon monoxide 49 - conversion to acyl complexes 20 - conversion to ketene complexes 49-55 - thermal extrusion 49-51 Carbonates, olefination 125, 127, 128, 132 Carbonyl complexes - reaction - with diazoalkanes 91

Index - with non-carbon nucleophiles

19, 20 with C-nucleophiles 15-17 - photolysis 41-45 Carbonyl methylenation 125-1 29 Carbonyl olefination 125-1 35 - mechanism 125-127, 134 Carbonyl ylides 206-2 13 - Experimental Procedure 2 10 Carboxamides - N-alkylation 194-196 - 0-alkylation 206, 207, 209-213 - carbonyl olefination 126, 128, 131 - conversion to aminocarbene complexes 22-24 - cyclization of 156-1 60 Carboxylic esters, carbonyl olefination 125-135 Carbyne complexes - as catalysts for alkyne metathesis 135, 137, 142 - conversion to carbene complexes 93-97 - cycloadditions 32, 102 - preparation 94, 95 - Experimental Procedure 95 - reactions with electrophiles 96, 97 - reactions with nucleophiles 32, 33, 94-96 Catalysts - for alkyne metathesis 13.5, 137, 142 - for cyclopropanation - with acceptor-substituted diazomethanes 174, 175, 220, 224 1 14-1 18 - with diazoalkanes - for enantioselective cyclopropanations 116, 174, 220, 224 - for enyne cyclization 149, 152, 153 - for olefin metathesis 5-8, 138-144 - enantiomerically pure 155 - heterogeneous 136, 138 - homogeneous multi-component 140 - homogeneous single-component 140144 - preparation, Experimental Procedures 80, 91 - polymer-bound 139 - poisoning 8, 114, 143, 144, 194, 197, 216 - for ring-fission of cyclopropanes 119, -

336

_I"

271

for ring-fission of cyclopropenes 119, 176 - see also Cobalt complexes, Copper complexes, etc. Catechol - 0-alkylation 199 - template for macrocyclizations 149 Ceric ammonium nitrate 39, 54, 55, 70 Chemical shifts 9-1 1 Chiral catalysts - see Catalysts Chiral ligands 175, 208, 220, 224 - see ulso Ligand Chloroiminium salts 21, 23 Chloromethyl phenyl sulfide 29-3 1 Chloronium ylides 21 8 Chromenes 156, 162, 222 Chromium arene tricarbonyl complexes 60 - from benzannulations 50, 52, 54 - Experimental Procedure 52 Chromium carbene complexes - benzannulation 49-55 - Experimental Procedures 52, 54 - cyclopentannulation 60-63 - cyclopropanation with 46-49, 70, 71, 106, 108, 115 - Experimental Procedure 48 - demetallation 39, 40, 42, 69 - photolysis 41, 4 3 4 5 , 64 - Experimental Procedure 45 - preparation 15-19, 22-24, 26, 34, 79 - Experimental Procedures 15, 23 Chromium(I1) chloride 128 Chromium complexes, as catalysts for diazodecomposition 115, 174 Chromium hexacarbonyl 15, 23 Claisen rearrangement 126, 127, I99 Cobalt carbene complexes 17 Cobalt complexes, as catalysts for diazodecomposition 174, 220, 224 Cocatalysts, for metathesis catalysts 139 Combinatorial chemistry - see Solid-phase synthesis Cope rearrangement 47, 70-73, 180 Copolymers 137, 141 Copper complexes - as catalysts for cyclopropanations 114116, 118-120 - as catalysts for diazodecomposition li4-116, 118, 174, 194 -

174, 220, 221, 224 Cross metathesis 16I , 164-1 67 - Experimental Procedure I61 - stoichiometric 167 Crowded complexes 78-82 Cumulenes 87, 101 Cuprates 36, 85 Cyanamides, reaction with carbene complexes 204 Cyanides - see Nitriles [2 + 21 Cycloadditions 7 - of alkenes to carbene complexes 103, 1 34- 1 68 - of alkynes to carbene complexes 46, 50, 51, 103, 135, 137 - of alkynylcarbene complexes 36 - of carbonyl compounds to carbene complexes 126, 134 - of ketene complexes 4 1, 44 Cycloalkenes - conversion to a,o-dienes 138 - heats of formation 145 - polymerizability by ROMP 145, 146 - by RCM 148-161 Cycloalkynes 135 Cyclobutadiene, ROMP of synthetic equivalents 146 Cyclobutanones - from enynes 46-48 - from ketene complexes 4 1, 44 Cyclobutenes - metathesis 103, 141, 146, 147, 167 - ROMP 146, 147 Cyclobutenones, from vinylcarbene complexes 52, 56, 57 Cycloheptadienes 70-72, 226, 229 Cycloheptadienones 63, 72 Cycloheptanones - by C-C insertion 193 - from vinylcarbene complexes, Experimental Procedure 73 Cycloheptatrienes 179, 180, 223 Cycloheptatrienylidenes 83 Cycloheptenes 148, 152-154 Cycloheptenones 63, 65 Cyclohexadienes 67, 69, 230 Cyclohexadienones 49, 67 - enantiomerically pure

Cyclohexanones by C-H insertion 190 - from sulfonium ylides 215 - from vinylcarbene complexes, Experimental Procedure 70 Cyclohexenes 148, 152, 153, 155 Cyclohexenones 68 Cyclometallation 92, 96 Cyclooctenes - by RCM 154, 155 - ROMP 136, 138, 140, 144, 145 Cyclopentadienes - from alkynylcarbene complexes 56, 59, 61 - cyclopropanation 108, 120 - ROMP 146 - from vinylcarbene complexes 56-60 Cyclopentannulation 56-66, 122-124, 150-152, 182-189 - Experimental Procedures 59, 6 I , 124, -

150

Cyclopentanones - from alkynes 62 - by C-H insertion 182-1 85 Cyclopentenes - from alkynes 168 - from heteroatom-substituted carbene complexes 66 - by RCM 146, 148, 150-152 - ROMP 141, 142, 144-146 Cyclopentenones - from cyclopropylcarbene complexes 65 - by C-H insertion 184, 185 - from vinylcarbene complexes 56, 6 I , 63 Cyclopropanation - with acceptor-substituted carbene complexes 2 18-226 - catalytic 105, 114-1 19, 218-226 - diastereoselective 6, 109, 115, 116, 219 - enantioselective 109, 111, 112, 116, 219-221, 223-226 - Experimental Procedures 221, 224 - with heteroatom-substituted carbene complexes 4 5 4 9 , 70-73 - intermolecular 105-1 19, 224-226 - intramolecular 46-48, 107, 220-224 - mechanism 7, 8, 114 - with non-heteroatom substituted carbene complexes 5-8, 105-1 19

Index vs. olefin metathesis 5-8 stoichiometric 6, 4 5 4 9 , 70-73, 105113 - Experimental Procedures 48, 106, I13 - theoretical treatments 5-8 - with titanium carbene complexes 8, 112, 113 - see ulso Alkynes, Arenes, Dienes, Enamines, etc. Cyclopropanes - as cocatalyst for olefin metathesis 138 - divinyl, Cope rearrangement 70-73, 180 - donor-acceptor-substituted, ringfission 226 - by C-H insertion 181, 182 - metal-catalyzed ring fission 119, 226 - from metallacyclobutanes 8 - vinyl, rearrangement to cyclopentenes 226 - see also Cyclopropanation Cycl opropen es - conversion to carbene complexes 99, 100, 102, 104, 119, 176, 177 - by cyclopropanation of alkynes 176, 218, 225 - cyclopropanation with 119 - Diels-Alder reaction 177, 222 - metathesis 146, 168 - preparation and rearrangement 176, 222, 227-229 Cyclopropenylidene complexes 86, 89 Cyclopropylcarbene complexes 19, 39, 42, 63, 66, 71 [2 + 21 Cycloreversion - of metallacyclobutanes 7, 100, 103, 138, 145, 148 - of metallacyclobutenes 100, 103, 137, 148 -

Dealkoxylation - see Abstraction

Degenerate olefin cross metathesis 136 Demetallation 37 Deprotonation - of alkyl complexes 78, 81, 82 - of carbyne complexes 95, 97 - of heteroatom-substituted carbene complexes 35, 68, 99

213

Desulfurization, of thiiranes 216 Dialkoxycarbene complexes 18 Diaminocarbenes 27-30 Diaminocarbene complexes - preparation 18, 22, 27-30, 33 - see also Heteroatom-substituted carbene complexes Diarylcarbene complexes - benzannulation 50 - cyclopropanations with 109 - metathesis 103 - preparation 90, 92, 103 - see ulso Non-heteroatom-substituted carbene complexes Diazoalkanes - acylation 173 - conversion to azines 116, 232 - conversion to 3H-pyrazolines 115, 218 114- cyclopropanation of alkenes with 118 - preparation of carbene complexes from 90-93 - reaction 105, 114, 172, 173, 197, - with acids 216 - with heteroatom-substituted carbene complexes 38, 42 - with hydroxy groups 15, 197 - with thiocarbonyl compounds 216 Diazoacetanilides 186, 187 Diazoacetic acid derivatives - see Acceptor-substituted diazomethanes Diazogroup transfer 172 Diazoimides, as precursors to carbonyl ylides 210-212 Diazoketones - see Acceptor-substituted diazomethanes Diazomethane 42, 9 1, 92 - 0-alkylations with 15 - cyclopropanations with 105, 106, 115-1 17 - see also Diazoalkanes Diazonium salts 15, 95 1,l-Dibromoalkanes - see I, 1 -Dihaloalkanes 1,2-Dichloroethane, abstraction of chloride from 218 Dicyclopentadiene, ROMP 136, 140, 142

214

Index

Diels-Alder reaction - of alkynylcarbene complexes

36, 54,

58, 60 - of cyclopropenes 177, 222 - of 2-pyranylidene complexes

55, 67, 69 of vinylcarbene complexes 36 - Experimental Procedure 70 Dienes - ADMET 148 - from alkynes 42 - by carbonyl olefination, Experimental Procedure 133 - by cross metathesis 161, 165 - cyclopropanation 47, 70-73, 108, 1 1 1, 120, 218, 222 - from diazoesters 181, 214 - from furans and pyrroles 230, 231 - RCM 148-161 - reaction with vinylcarbene complexes 226, 229 - see also Diels-Alder reaction 1,l-Dihaloalkanes - carbonyl olefination with 127-129, 132, I33 - Experimental Procedure 133 - conversion to carbene complexes 89, 91 - conversion to carbyne complexes 94, 95 - Experimental Procedure 95 Dihydroazepines 71, 72, 159 Dihydrofurans - from acylcarbene complexes 226-228 - Experimental Procedure 227 - from carbonyl ylides 207, 209 - by RCM 162 - reaction with acylcarbene complexes 228 2,3-Dihydro-lH-imidazole-2-ylidenes 1 8, 22, 28, 30 Dihy dropyrans - from alkoxycarbene complexes 48, 68 - by carbonyl olefination 134 - cyclopropanation 223, 225 - by RCM 153, 156, 161, 162 Dihydropyridines 16, 45, 53, 229 1,2-Dihydropyridin-2-ylidenes 2 1 Dihydropyrroles - from 4-amino-1-butynes 168 - cyclopropanation 225 - by RCM 157, 158 - from pyrroles 225 -

2,3-Dihydrothiazol-2-ylidenes23 Dimethyl acetylenedicarboxylate (DMAD) - benzannulation 53 - as dipolarophile 203, 204, 211, 213 Dimethyl sulfoxide, as oxidant 39, 40 (Dimethylsu1fonium)methyl complexes 87, 106, 111, 123, 124 Dimethyltitanocene 127, 128 Dioxolanes, from carbonyl ylides 206, 209, 212 Diphenylacetylene 48, 63 Diphenylcarbene complexes - see Diarylcarbene complexes Diphenylcyclopropane 106 Diphenylisobenzofuran 176 1,3-Dipolar cycloaddition - to alkenyl/alkynylcarbene complexes 36, 37 - of carbonyl ylides 208-213 - Experimental Procedure 210 - of diazo compounds 115, 218 - formal, of acylcarbene complexes 226229 Disodium pentacarbonylchromate 23, 24 Disproportionation of carbene complexes 86 1,3-Dithianes - see Dithioacetals Dithioacetals - carbonyl olefination 128, 129, 132, 133 - as precursors for titanium carbene complexes 1 12, 167 - Experimental Procedures 113, 133 Divinylaziridines 7 1 Divinylcyclopropanes 70, 7 1, 180, 226 Dotz benzannulation 49-55 - Experimental Procedures 52, 54 - mechanism 49-52 - natural product synthesis 52 - scope and limitations 49-52 Electrocyclization of l-metalla-l,3,5-trienes 57 - of trienes 230 Electronic structure of carbene complexes 1-5 Electrophilic carbene complexes 1 - see also Acceptor-substituted carbene complexes P-Elimination 82, 84, 86, 124 -

Index

Enamines by carbonyl olefination 126, 128, I31 - cycloaddition to ketene complexes 44 - cyclopropanation 115, 218 - as dienophiles 55, 67, 69 - olefin metathesis 34, 144 - reaction with alkynylcarbene complexes 36, 58, 61 Enol ethers - from acrolein acetal, Experimental Procedure 205 - from alkoxycarbene complexes by thermolysis 39, 48, 68 - from alkoxycarbene complexes and ylides 42, 43 - by 0-alkylation of carbonyl compounds 206 - by carbonyl olefination 125-135 - Experimental Procedures 129, 133 - cycloaddition to ketene complexes 44 - cyclopropanation 106, 108, 109, 115, 118, 120, 218, 222, 223, 225-227 - as dipolarophiles 2 11 - olefin metathesis 33, 34, 143, 144, 151, 153, 162 - reaction with acylcarbene complexes 226 Enynes - conversion to cyclobutanones 46-48 - cyclopropanation 46-48 - cyclization 46, 149, 152, 153, 155, 158-160, 162 Episulfides - see Thiiranes Epoxides - see Oxiranes Eschenmoser thiocarbonyl olefination 216 Esters - see Carboxylic esters Ethene - see Ethylene Ethers - 0-alkylation by carbene complexes 205 - by carbene 0 - H insertion 196-198 - cyclic, formation by RCM 149, 162 - hydride abstraction from 31, 232 - macrocyclic 149, 163, 207, 223 - as solvents for benzannulations 50, -

JL

275

Ethyl cyanoacetate 95 Ethylaluminium dichloride - as catalyst for olefin metathesis 138, 140 Ethylene - cross metathesis with alkenes 137, 155, 161, 162 - cross metathesis with alkynes 165 - oligomerization I37 - production 136, 137 - as volatile byproduct of RCM/ADMET 143 Exchange metathesis 135, 136 Fischer-type carbene complexes 1-7, 13 - as metathesis catalysts 140, 153 - preparation, Experimental Procedures 15, 23, 29, 86 - see also Heteroatom-substituted carbene complexes Fluorobenzene 191, 228 Formamides, conversion to aminocarbene complexes 23 Forster reaction 172 Fredericamycine 5 1 Fullerenes, cyclopropanation 2 18 Fumarates, cyclopropanation 48, 115, 120 - Experimental Procedure 48 Furanones - from alkoxycarbene complexes 39, 57, 62 - from ally1 diazoacetates 221, 228, 229-23 1 - from carbonyl ylides 209, 212 - by C-H insertion 187-189, 232 - by 0-H insertion 198 - from oxonium ylides 206, 207 Furans 42, 21 1 - from acylcarbene complexes 21 1, 227-229 - Experimental Procedure 227 - from alkoxycarbene complexes 65 - benzannulation 54 - reaction with acylcarbene complexes 228, 230, 231 - ring fission 230, 231 - from vinylcarbene complexes 52, 56, 57, 60

276

Index

Germanes 121 Grignard reagents 88, 109 Griseofulvin 205 Hafnium carbene complexes 121 Halides, abstraction 29, 31, 217 Halo alcohols, reaction with carbonyl complexes 18 Halo ethers, reaction with metallates 85 Halo thioethers 29-3 I , 87, 88, 107 Hard and soft transition metal complexes 144 Heterogeneous metathesis catalysts 138 Homogeneous metathesis catalysts 6, 140-144 Hydrazones 172 Hydride abstraction - by carbene complexes 31, 178, 197, 232 - for preparation of carbene complexes 29, 31, 83 Hydride complexes 89, 102 Hydrolysis, of alkoxycarbene complexes 39 Imidazol-2-ylidenes 18, 22, 28, 30 Imines - cycloaddition to vinylidene complexes 25, 27 - a-halo 21-23 - C-H insertion into 184 - olefination 131 - reaction with carbene complexes 72, 202, 203 - reaction with carbyne complexes 32 - reaction with ketene complexes 41, 44, 64 - reaction with propargyl complexes 65 Indanones - from alkoxycarbene complexes, Experimental Procedure 6 1 - by C-H insertion 184, 221 Indenes - from acylcarbene complexes 189 - from alkynylcarbene complexes 58, 60 - from heteroatom-substituted carbene complexes 49, 50, 52 Indenones, from acylcarbene complexes 177, 184, 191, 215, 225

Indoles - alkylation by C-H insertion

191, 192 - Experimental Procedure 192 - from 2-alkynylanilines 53, 60, 168 - benzannulation 44, 55, 68, 191 186, - by intramolecular C-H insertion 187 - Experimental Procedure 187 - reaction with acylcarbene complexes 191, 192, 228 Indolizines 203 C-H Insertion - of acceptor-substituted carbene complexes 179-192 - Experimental Procedures 182, 187, 192 - enantioselective 180, 183, 184, 186, 188-191 - of heteroatom-substituted carbene complexes 65 - of imido complexes 121 - intermolecular 189, 191, 192 - intramolecular 107, 122-124, 179 - mechanism 119, 122 - of non-heteroatom-substituted carbene complexes 107, 119, 121-125 - Experimental Procedure 124 - regioselectivity 179 - stereoselectivity 180 C-C Insertion 193 C-N Insertion 198 C-0 Insertion 205 C-S Insertion 214 N-H Insertion 193-196 0-H Insertion 193, 196-199 - Experimental Procedure 197 S-H Insertion 193, 197, 200 Si-H Insertion 192 Iodoform 128 Iodonium ylides - from acylcarbene complexes 218 - as carbene complex precursors 176, 190, 195 Iridium carbene complexes 92 Iron carbene complexes - heteroatom-substituted 107 - benzannulations 53 - cyclopentannulations 60 - preparation 18-23, 26-31, 34

Index non-heteroatom-substituted cyclopropanation 6, 106, 109-1 12, 115, 116, 118 - enantiomerically pure 109, 1 1 1, 1 12 - C-H insertion 107, 122-124 - preparation 83, 85-89, 99, 101, 106, 109 - stability 75, 87, 99 Iron complexes, as catalysts for diazodecomposition 112, 115, 174 Isobutene, cyclopropanation 224 Isonitrile complexes - conversion to carbene complexes 21, 22 lsonitriles 33 -

-

KDO (3-deoxy-D-manno-2-octulosonic acid) 208, 210 Ketene acetals - from carbonyl ylides 207 - by olefination of carbonates 125, 127, 128, 132 - reaction with alkoxycarbene complexes 66 Ketene complexes - from carbene complexes by photolysis 41, 4 3 4 5 - Experimental Procedure 45 - [2 + 21 cycloadditions 41, 43, 44 - as intermediates in benzannulations 4 1, 44, 49-52 - reactions with nucleophiles 41, 43, 4.5, 67, 71, 72 Ketenes 60 Ketocarbene complexes - see Acceptor-substituted carbene complexes Ketones - 0-alkylation 206. 21 1, 212 102 - conversion to carbene complexes - olefination 125-134 - Experimental Procedure 133 - reaction with metallates 85 Lactams, by RCM 149, 157-160 P-Lactams - N-alkylation 194-196 - conversion to carbene complexes 24 - from heteroatom-substituted carbene complexes 40, 44

211

- by intramolecular C-H insertion

179, 181-1 83 - Experimental Procedure 182 - norbornene derivatives, ROMP 147 - transformations 159, 160, 166, 199 Lactones - by C-H insertion 181, 183, 188-190 - macrocyclic 149, 160, 163, 207, 223 - by RCM 149, 160, 163 Ligands - enantiomerically pure 175, 208, 220, 224 - exchange 33, 102, 175 - C,-symmetric 208, 220, 224 Living polymerization 141 - alkynes 135, 137 - terminating agents 141, 143, 144 Lombard0 reagent 127, 128 Macrocyclization - of diazo carbonyl compounds

207, 223 of dienes by RCM 149, 160, 163 Manganese carbene complexes - heteroatom-substituted 17, 18, 20, 27, 32, 68 - non-heteroatom-substituted 87, 90, 96, 99 Meerwein salt - see Trialkyloxonium salts Metallacyclobutanes 6, 7, 104, 134, - by [2 + 21 cycloaddition 143, 148 - reaction with carbonyl compounds 128, 130 - thermolysis of 7 Metallacyclobutenes 46, SO, 103, 104, 137 Metallacyclohexadienes 57 Metallacyclopentenes 17, 34, 102 Metallates 18-24 - generation 19, 88 - reaction - with alkylhalides 20, 88 - with carbonyl compounds 85 - with carboxamides 22-24 Metathesis - see Olefin metathesis Methylenation, of carbonyl compounds 125-129 Methyllithium - see Organolithium compounds -

278

Index

Methyltrioxorhenium 139, 154, 174 Molecular orbitals of carbene complexes 2-5 Molybdenum-based metathesis catalysts 6 - enantiomerically pure 155 - heterogeneous 136, 139 - homogeneous 141, 143, 150, 156, 161, 165 Molybdenum carbene complexes 6 - heteroatom-substituted - cyclopropanation with 47, 48 - preparation 16, 20, 100 - reaction with alkynes 42, 47, 48, 53, 61, 72 - reaction with 2-aza-l,3-dienes 61 - non-heteroatom-substituted - carbonyl olefination 129, 131, 134 - cyclopropanations with 106, 108 - preparation 79-81, 86, 95, 97. 100, 101 Morpholinones - from azomethine ylides 203 - from carbonyl ylides 213 - by 0-H insertion 43, 198 - by Stevens rearrangement 201 Musk perfume 138 Naphthols - by benzannulation

44, 49-55 by C-H insertion 190 Naphthyldiazomethane 1 16 Natural product synthesis 51, 122, 160, 163, 206, 221, 226 Neohexene 108, 138 Neopentane, elimination 78, 79, 82 Neopentylidene complexes 75, 78, 79, 81, 82, 121 Nickel carbene complexes - cyclopropanations with 111 - preparation 18, 88 Nickel complexes - as catalysts for cyclopropanations 116, 119 - ethylene oligomerization with 137 Nitrile ylides 203 Nitriles - N-alkylation by carbene complexes 203 - reaction with Tebbe reagent 126 NMR, of carbene complexes 9-1 1 Non-productive olefin metathesis 136 -

Norbomenes - ring-opening cross metathesis 166 - ROMP 136, 138, 140-142, 145, 147 Norsorex 138 Nuclear magnetic resonance 9-1 1 Nucleotides, norbornene derivatives, ROMP 147 Nysted reagent 128 Olefin metathesis

134-168 138-144 - heterogeneous catalysts 138-140 - homogeneous catalysts 140-144 - industrial applications 136-138, 144147 - light-induced 103, 138, 140 - mechanism 5-8, 100, 137, 145, 148 - preparation of heteroatom-substituted carbene complexes by 33, 34 - stoichiometric 134, 165, 167 - theoretical treatment 5-8 Olefins - see Alkenes Oligoacetylenes 135 Orbitals, molecular 2-5 Organoaluminium compounds, as cocatalysts for olefin metathesis 138-141 Organolead compounds, as cocatalysts for olefin metathesis 139, 140, 150 Organolithium compounds - as cocatalysts for olefin metathesis 139 - reaction - with carbonyl complexes 15-17, 37, 100 - with carbyne complexes 94, 96 - with heteroatom-substituted carbene complexes 36, 38, 42, 65, 68, 84, 107, 109, 124 - with non-heteroatom-substituted carbene complexes 83 Organomagnesium compounds - see Grignard reagents Organotin compounds - see Stannanes Osmium carbene complexes, preparation 22, 81, 92, 96, 97, 102 Osmium complexes, as catalysts for diazodecomposition 174 7-Oxanorbornene derivatives, metathesis 146, 147, 166 - choice of the catalyst

Index Oxazoles alkylation by C-H insertion 190 - from nitriles and carbene complexes 203 Oxazolidines 203, 2 1 1 , 2 12 Oxepanes 72, 190, 198, 207 Oxepines, preparation by RCM 156, 163 Oxidation - of arene complexes 52-54 - of heteroatom-substituted carbene complexes 3 7 4 0 - of metallacyclobutanes 8 - see ulso Hydride abstraction Oxidative insertion 77 Oximes 71, 172, 203 Oxiranes 206, 209, 21 1, 213 - from carbonyl ylides - reaction with vinylcarbene complexes 68 - from sulfonium ylides 214 Oxonium ylides 205-208 Oxophilic species, early transition metals as 144 Oxygen, stability of carbene complexes towards 144 -

Palladium complexes as catalysts for diazodecomposition 114, 115, 117, 174 - as catalysts for enyne cyclization 149 Pantolactone 192, 219 Pauson-Khand reaction 36 Peptides, by acylation with ketene complexes 43 Peptoids 43, 149, 159, 160 Phenols - 0-acylation by ketene complexes 43 - addition to alkynylcarbene complexes 36 - 0-alkylation by carbene complexes 199 - preparation 41, 44 Phenylacetylene 230 Phenylalanine 178, 187, 223 Phenylcarbene complexes - Experimental Procedure 91 - see ulso Non-heteroatom-substituted carbene complexes Phenyldiazomethane 91, 1 18 Phenylthiomethyl iron complexes - as carbene complex precursors 29, 88, 107, 123 -

279

preparation, Experimental Procedures 29, 124 Phillips Triolefin Process 137 Phosphines - alkylation 217 - stabilization of carbene complexes by 104 Phosphorus ylides 9, 125 - conversion to non-heteroatom-substituted carbene complexes 93 - generation 217 - reaction with carbene complexes 38 - reaction with ketene complexes 41, 43 Photo1ysis - of alkyl complexes 33, 34, 82 - of carbene complexes 41, 4 3 4 5 , 103 - Experimental Procedure 45 Piperidines 43, 48, 64, 209 Piperidinones - from 1 -amino-4-pentynes 68 - from ammonium ylides 45, 201 - by Diels-Alder reaction 60 - by N-H insertion 195 Platinum complexes 2, 23, 26 - as catalysts for diazodecomposition 174 152 - as catalysts for enyne cyclization Polyacetylene 135, 137 Poly(cyc1ooctene) 138, 144 Poly(cyc1opentene) 144 Polyenes 146 Polymer-supported metathesis catalysts 139 Polymeric supports - see Solid-phase synthesis Polymerization - see Ring-opening polymerization, Ziegler-Natta-polymerization Polynorbornene derivatives 146, 147 Propargyl complexes 65, 84 Propargyl halides - conversion to vinylcarbene complexes 89 2-Pyranones 39, 67 2H-Pyran-2-y lidenes - preparation 20, 26, 27, 67-69 - Diels-Alder reaction 55, 67 Pyrazolines 1 15, 2 18 Pyridines - from 2-aminovinylcarbene complexes 67, 69 -

280

Index

203 Pyrroles - alkylation by C-H insertion 186, 190 - from 4-amino- I-butynes 168 - cyclopropanation 225 - from dihydrofurans 226 - from heteroatom-substituted carbene complexes 60, 63, 65 - from nitrile ylides 204 - reaction - with alkoxycarbene complexes 35 - with vinylcarbene complexes 229, 230 - ring fission by acylcarbene complexes 230, 231 Pyrrolidines - ring expansion 43 - preparation 47, 48, 55, 223, 225 Pyrrolidinones - from 1 -amino-3-butynes 62 61 - from 2-aza- 1,3-dienes - conversion to aminocarbene complexes 24 - by C-H insertion 183, 186, 187 - by N-H insertion 195 - by Stevens rearrangement 64, 201 Pyrrolizines 64, 157, 183, 186, 223, 228 - N-alkylation

Quaternary ammonium salts - see Ammonium ylides

Quinones 52-54 - Experimental Procedure

54

Radicals in oxonium ylide rearrangements 205 - addition to vinylcarbene complexes 36, 67 Reduction - of carbyne complexes 94, 96 - of heteroatom-substituted carbene complexes 37, 42, 46 Reductive elimination 38, 57, 59, 77 Retention of configuration, in C-H insertions 180, 184 Retro-Diels-Alder reactions 55, 67 Rhenium carbene complexes - heteroatom-substituted 17, 27, 32 - non-heteroatom-substituted - in olefin metathesis 142 - preparation 79, 81-83, 87, 96, 101 -

Rhenium complexes, as catalysts for - diazodecomposition 174, 217 - olefin metathesis 139, 142, 147

Rhodium carbene complexes 30, 92, 177 Rhodium(I1) carboxylates 114, - as catalysts for diazodecomposition 118, 174 - enantiomerically pure 174-176, 220, 221, 224 Ring-closing metathesis (RCM) 135, 137, 148-1 63 - asymmetric 155 - effect of monomer concentration on 148 - Experimental Procedures 150, 156 - preparation of carbocycles 150-155 - preparation of heterocycles 156-163 - on solid supports 151, 156, 159, 162, 166 - stereoselectivity 155 - thermodynamics 144-146, 148 Ring-opening cross metathesis 166-168 Ring-opening metathesis polymerization (ROMP) 136, 138, 141, 144-148 - effect of monomer concentration on 145-147 - functionalized polymers from 146, 147 - living 141 - side reactions 147 - stereoselectivity 147 - thermodynamics 142, 144-146 Ruthenium carbene complexes - as catalysts for olefin metathesis 139, 142-144, 149, 150, 156 - enantiomerically pure 109 - C-H insertion 121 - preparation 17, 26, 89, 91, 99, 101-103 Ruthenium complexes - as catalysts for diazodecomposition 174, 217, 224 - as catalysts for olefin metathesis 140, 142, 152, 153 - see also Ruthenium carbene complexes Schiff bases - see Imines

Schrock-type carbene complexes 1-7 preparation, Experimental Procedures 80, 91 - see also Non-heteroatom-substituted carbene complexes -

Index Self metathesis 136 Semicarbazones 172 Serine, etherification 196, 197 - Experimental Procedure 197 Shell Higher Olefin Process (SHOP) 137 Sigmatropic rearrangements 43, 45, 200, 205-207, 214 - Experimental Procedures 45, 205 - see also Cope-, Claisen rearrangement Sil ane s - in benzannulations 53, 54 - C-H insertion 191 - Si-H insertion 121, 122, 192 Simmons-Smith reagent 106, 115 Sodium amalgam 30 Sodium dicarbonyl(cycIopentadieny1)ferrate 19, 29-31 Sodium naphthalenide 23 Solid-phase synthesis - 1 $dipolar cycloaddition 2 1 1 - 0-H insertion 199 - olefin metathesis 1.51, 156, 159, 162, 166 - synthesis of peptides 41 Solvents - for benzannulations 49, 50 - for olefin metathesis 143, 144, 146, 147 Stable carbenes 27-30 Stannanes 138- as cocatalysts for olefin metathesis 140 - reaction with carbene complexes 38,40, 121 Stevens rearrangement 43, 45, 64, 198, 200-202 - Experimental Procedure 200 Stoichiometric cyclopropanations 6, 45-49, 106-1 I3 Stoichiometric olefin metathesis 103, 134, 165, 167 Styrenes 161, 164, 166 - cross metathesis 108-1 1 1, 113, 11 8, - cyclopropanation 218 Sulfides - see Thioethers Sulfonyl azides 172 N-Sulfonyl hydrazones 173 Sulfoxonium-ylides 176

281

Sulfur ylides

2 1 3-2 16 as carbene complex precursors 176, 195 - cyclopropanations with 116, 120, 214 - enantiomerically pure 216 - from acylcarbene complexes -

Tacticity, of polymers prepared by ROMP 147 Tandem carbonyl olefination/Cope rearrangement 126 Tandem carbonyl ylide formation/l,3dipolar cycloaddition 208-2 13 Tandem olefin metathesis/carbonyl olefination 134 Tandem ring-opening/ring-closing metathesis 150, 153, 155 Tantalum carbene complexes - carbonyl olefination 129, 13 1 - C-H insertion 121 - olefin metathesis 142 - preparation 78, 79, 81, 82, 103 - stability 75, 78 - theoretical treatments 3-5, 78 Tebbe reagent - carbonyl olefination 125-1 29, 134 - Experimental Procedure 129 - conversion to titanium carbene complexes 104 - higher homologs 129, 130 - in situ preparation, Experimental Procedure 129 Tetraethyllead - as cocatalyst for olefin metathesis 139, 150, 151 Tetrahydroazepines - see Azepines Tetrah ydrofurans - from alkoxycarbene complexes 39 - by cycloaddition 21 1 - by C-H insertion 188 - by C-0 insertion 208 - by 0-H insertion 198 156, 166 - by olefin metathesis - reaction with acylcarbene complexes 190, 191 Tetrahydroisoquinolines 201, 210

Tetrahydro-2-pyranylidenes -

conversion to vinylstannanes demetallation 39 preparation 26, 27, 68

42

282

Index

Tetrahydropyridines - from 1-amino-4-pentynes 168 - by RCM 158, 159 Theoretical treatments - cyclopropanation 7, 8 - benzannulation 49-52 - Fischer-type/Schrock-type carbene complexes 3-5 - olefin metathesis 5-8 Thermodynamics - of carbene complex formation 78 - of carbonyl olefination 127 - of ROMP 144-147 Thermolysis - of heteroatom-substituted carbene complexes 37-39, 42, 49, 50 - of metallacyclobutanes 7, 100, 104, 153 Thiiranes - S-alkylation 216 - from thiocarbonyl compounds 2 16, 217 Thioacetal s - S-alkylation 214, 215 - see also Dithioacetals Thiocarbonyl ylides 21 6 Thioester, olefination 128, 132 Thioethers - a-abstraction 87, 106, 109, 111-113 - S-alkylation 21 3-2 16 - enantiomerically pure 2 16 - olefin metathesis 143 Thioketenes 2 17 Thiols - addition to alkynylcarbene complexes 36 - S-alkylation by acylcarbene complexes 197, 200 - poisoning of catalysts by 194, 197 Thiophenes, alkylation by C-H insertion 184, 191 Thiophenium ylides 176 Thiophenols - see Thiols Ti tanacyclobutanes - preparation 7, 8, 92, 104 - reaction with carbonyl compounds 128. 130 - thermolysis 7, 104, 153 Titanacyclobutenes 104, 130

Titanium carbene complexes carbonyl olefination 125-1 35 - Experimental Procedures 129, 133 - cyclometallation 92 - cyclopropanation with 112, 113 - Experimental Procedure I 13 - generation 30, 92, 100, 104, 125-135 - C-H insertion 121 - olefin metathesis 7, 8, 134, 153 Titanium tetrachloride 127, 128 Titanocene dichloride 112, 113, 125, 128, 132, 133, 167 Tosyl azide 172 Trialkyloxonium salts 15-19, 107, 109 Triazoles - from diazoacetamides 172 - conversion to diazoalkanes 173 Trienes, RCM 152, 153, 155, 157, 162 Triflates 15, 16 Triolefin process 137 Tropylidene complexes 83 Tungstacyclobutanes 7 Tungsten carbene complexes - heteroatom-substituted - benzannulations 55 - conversion to - azepinones 72 - furans 65 - pyrroles 65 - cyclopentannulations 58-61 - oxidation 39, 40, 70 - preparation 15-19, 22, 24, 26, 27, 32, 68 - reaction with diazoalkanes 42, 91, 174 - reaction with dihydropyridines 46 - reduction 39 - thermolysis 42, 47 - non-heteroatom-substituted - carbonyl olefination 129, 131 - cyclopropanations with 6, 106, 108, 109, 111 - enantiomerically pure 109, 111 - C-H insertion 121 - olefin metathesis 6, 75, 140-142, 153 - preparation 83, 84, 86, 88, 89, 93, 97, 99, 102, 103 - stability 75 Tungsten carbyne complexes 97, 135, 142

-

Index Tungsten-based metathesis catalysts 136, 139-142, 150, 167 - see ulso Tungsten carbene complexes, Tungsten carbyne complexes Unsaturated carbonyl compounds see Acceptor-substituted alkenes

-

Vanadium carbene complexes 23, 79 Vestenamer 138, 144 Vinyl complexes, reaction with electrophiles 98 Vinyl iodides - cyclopropanation 2 18 - preparation 128 Vinylcarbene complexes, heteroatomsubstituted - from alkylcarbene complexes 35, 36 - from alkynes 26, 27 - from alkynylcarbene complexes 36, 56, 58, 62 - from carbonyl complexes 16, 17, 56 - cyclopropanation 36, 70-73 - as dienophiles 36, 37, 69, 70 - from metallates 21 - as Michael-acceptors 36, 37 - by olefin metathesis 34 Vinylcarbene complexes, non-heteroatomsubstituted - by &abstraction 83, 84, 87, 89 - from acceptor-substituted vinyldiazomethanes 199, 218, 222, 225, 229-231 - from alkynes 46, 49, 50, 103, 177 - from carbyne complexes 96, 97 - cycloadditions 222, 227, 229, 230 - from cyclopropenes 102, 177 - from ylides 93 I-Vinylcycloalkenes, from enynes 46, 149, 152, 153, 155, 158-160, 162 Vinylcyclopropanes - preparation 46-48, 108, 11 1-113, 118, 120, 2 17, 222, 225 - rearrangement to cyclopentenes 226

283

Vinyldiazoacetic esters 192, 199, 222, 225, 227, 229-231 Vinylidene complexes - from acyl complexes, Experimental Procedure 86 - from alkenyl complexes 81 - from alkynes 25, 98, 101, 169 - from alkynyl complexes 25, 98-100 - from carbyne complexes 95-97 - Experimental Procedure 95 - cycloadditions 99 - as metathesis catalysts 142 - reaction - with electrophiles 97 - with nucleophiles 25-27 Vinylketene complexes - as intermediates in benzannulations 44, 49-5 1 - intramolecular acylations by 44, 62-64 - preparation 41, 44, 48, 63 Water, as solvent for olefin metathesis 146 Wolff rearrangement 183

144,

Ylides

90-93, 172-176 - preparation 198-21 8 - reaction - with acylcarbene complexes 232 - with alkoxycarbene complexes 38, 42, 43 Ynamines 58 - as carbene complex precursors

Ziegler-Natta catalysts, for olefin metathesis 136 Ziegler-Natta polymerization 147 Zinc halides 105, 114 Zirconium carbene complexes 100, 104, 129, 131 Zirconocene dichloride 128 Zwitterions 57-59

Metal Carbenes in Organic Synthesis

Metal carbenes in organic synthesis

Metal carbenes in organic synthesis