Houben-WeylMethods of Organic ChemistryAdditional and Supplementary Volumes to the 4th EditionEditorial Board: K.H. Büchel, J. Falbe, H. Hagemann, M. Hanack, D. Klamann, R. Kreher, H. Kropf, M. Regitz, E. Schaumann

Publication Year1997

ISBN (Print)978-3-13-798204-3

Vol. E 17 b

Cyclopropanes: Synthesis

METHODS OF

ORGANIC CHEMISTRY

METHODS OF ORGANIC CHEMISTRY

(HOUBEN-WEYL)

ADDITIONAL AND SUPPLEMENTARY VOLUMES TO THE 4TH EDITION

EDITORIAL BOARD

K.H. Büchel J. Falbe H. Hagemann Leverkusen Düsseldorf Leverkusen

M. Hanack D. Klamann R. Kreher Tübingen Hamburg Dortmund

H. Kropf M. Regitz E. Schaumann Hamburg Kaisersla utern Clausthal

EDITORIAL OFFICE

J.Y. Rowden

L. A. Sturdy . S. R. Thornton Stuttgart

GEORG THIEME VERLAG STUTTGART . NEW YORK

VOLUME E17b

CARBOCYCLIC THREE- AND FOUR­MEMBERED RING COMPOUNDS

Editor

Armin de Meijere Göttingen I Germany

Authors

R.J. Bushby N. De Kimpe Leeds I Great Britain Gent I Belgium

A. de Meijere P. Eilbracht z. Goldschmidt A.J.H. Klunder Göuingen I Germany Dortmund I Germany Ramat-Gan I Israel Nijmegen I The Netherlands

S. I. Kozhushkov P. Margaretha J.-L. Ripoll J. Salaün Göuingen I Germany Hamburg I Germany Caen I France Orsay Cedex I France

J. Seibe1 A. Stolle L.K. Sydnes E. Vilsmaier Wiesbaden I Germany Wuppertal I Germany Bergen I Norway Kaiserslautern / Germany

S. von Angerer Pentling I Germany

J.L. Wolk Ramat-Gan / Israel

B. Z wanen burg Nijmegen I The Netherlands

19197 GEORG THIEME VERLAG STUTTGART . NEW YORK

This book mentions numerous commercial and proprietary trade names, registered trademarks and the like (not necessarily marked as such), patents, production and manufacturing procedures, registered designs and designations. The Editors and Publishers wish to point out very clearly that the present legal situation in respect of these names or designations or trademarks must be carefully examined be fore making any commercial use of the same. Industrially produced apparatus and equipment are included to a necessarily restricted extent only and any exclusion of products not mentioned in this book does not imply that any such selection of exclusion has been based on quality criteria or quality considerations.

Die Deutsche Bibliothek - CIP-Einheitsaufnahme

Methoden der organischen Chemie / (Houben-Weyl). -Stuttgart ; New York : Thieme

Teilw. begr. von Eugen Müller und OUo Bayer. - Teilw. begr. von Eugen Müller ... Fortgef. von Heinz Kropf. - Erw.- und Folgebd. zur 4. Aufl. hrsg. von K. H. Büchel ... - Teilw. u.d. T.: Methods of organic chemistry

NE: Müller, Eugen [Hrsg.]; Houben, losef [Hrsg.]; Kropf, Heinz [Hrsg.]; Büchel, Karl H. [Hrsg.]; Methods of organic chemistry

Additional and suppl. vol. of the 4. ed. Vol. E 17b. Carbocyclic three- and four-membered ring compounds / ed. Armin de Meijere. Authors M. S. Baird ... - 1996

NE: Meijere, Armin de [Hrsg.]; Baird, Mark S.

Library of Congress Card No.: applied for

Date of publication 18.09.1996

Copyright and all related rights reserved, especially the right of copying and distribution, multiplication and reproduction, as well as of translation. No part of this book may be reproduced by any process, whether by photostat or microfilm or any other procedure, without previous written consent by the Publisher. This also includes the use of electronic media of da ta processing on reproduction of any kind.

© 1997, Georg Thieme Verlag, Rüdigerstraße 14, 0-70469 Stuttgart - Printed in Germany

Typesetting and Printing: Tutte Druckerei GmbH, 0-94119 Salzweg-Passau

ISBN 3-13-798204-9

Preface

Methods of Organic Chemistry - or synonymously Houben-Weyl- would be severely incomplete in this decade without the coverage of sm all ring chemistry. The first, and only, Houben-Weyl volume on Carbocyc1ic Three- and Four-membered Ring Compounds was published 25 years ago. Until that time small ring chemistry was, in the main, considered a domain for mechanistic and physical organic investigations, although many of the basic preparative methods had already been developed and the majority of important transformations thoroughly studied and reasonably well understood. Nevertheless, the notion, which started to evolve slowly in the sixties, of small ring compounds being useful and, frequently, uniquely applicable building blocks for other carbocyc1ic and also acyc1ic organic skeletons, has only since fully matured.

Quite a number of cyc1opropane and cyc10butane derivatives have gained importance in their own right. For instance, the cyc1opropyl group has turned out to be an essential feature in natural and non-natural products with insecticidal, cytostatic, various plant physiological, as well as antiinfective, activities and has, therefore, entered the realm ofindustrially applied chemistry. Arecent survey listed 191 pharmaceutically impor­tant compounds containing an aminocyc1opropane substructure, the best known example being the widely used broad-spectrum antibiotic Ciprofloxacin.

Yet the discovery of new types of natural sm all ring compounds continues. For example, a few years ago an antibiotic natural product with an unusual fatty acid side chain containing four adjacent cyc1opropyl groups was described, and more re­cently, a similar compound with five adjacent, and a total of six, cyc1opropyl groups has been reported. The vast progress in the development of stereoselective synthetic methodology (see Houben-Weyl Volume E21) has also brought ab out new methods for stereoselective cyc1opropanations, and this has gone hand in hand with efforts towards enantioselective total syntheses of cyc1opropyl-group-containing natural and non-natural products. So far these developments have only scratched the surface, as most ofthese methods are still hampered by severe constraints, and so the race goes on.

In view ofthis progress, it appeared to be time to publish an up-to-date comprehensive treatment of the methods of preparation and transformation of carbocyc1ic three­and four-membered-ring compounds. Certainly, the access to cyc1opropane deriva­tives via carbene additions to alkenes, which represents one of the most general methods, has been covered - albeit from a different perspective - in the Houben-Weyl volume on Carbenes (E19b), and cross-references are frequently made to Houben­Weyl E19b in the corresponding sections of this volume. Yet this earlier volume cannot even be considered to be a comprehensive summary of the methods for the synthesis of cyc1opropanes, let alone ofthe preparations and transformations of cyc1opropenes, cyc1oproparenes, cyc1opropenones and triafulvenes, all of which are covered here.

Twenty five years ago, all of the material on cyc1opropane and cyc10butane chemistry was compiled by two single authors, which at the time must have been a truly Her­culean task. Nowadays, this would simply be impossible. Thus, Houben-Weyl E17 has come to li fe only through the joint efforts of more than 60 authors, some of whom have invested a lot of their time with major contributions. An estimated 20,000

VI Preface Houben-Weyl

publications were read and evaluated, well over 13,000 references actually being quoted in the three-membered-ring sections alone. An editorial staff of 6 native speakers took care to make the presentation uniform and polish the language, espe­cially of the non-native English writing authors. All the art work was redrawn by a group of 4.

The editor is indebted to all the authors, the editorial staff and the artists for the fruitful collaboration which made this book possible. We all hope that this handbook will serve the chemie al community well and will become an indispensable reference tool for those engaged in Synthetic Organic Chemistry.

Göttingen, August 1996 Armin de Meijere

Volume E 17a

Introduction

1.

A.

Volume E 17b

1.

A.

Volume E 17c

1.

B. C.

Volume E 17 d

2.

A. B. C.

3.

A. B. C.

4.

A. B.

5.

A. B. C.

Contents to all Volumes

CycIopropanes

Synthesis

CycIopropanes

Synthesis (continued)

CycIopropanes

Transformations Coordination Chemistry

CycIopropenes

Synthesis Transformations Coordination Chemistry

CycIoproparenes

Synthesis Transformations Coordination Chemistry

Triafulvenes, Calicenes and QuinocycIopropenes

Synthesis Transformations

CycIopropenone and Heteroanalogs

Synthesis Transformations Coordination Chemistry

VIII

6.

A. B. C.

Volume E 17e

7.

A. B. C.

Volume E 17f

8.

A. B. C.

9.

A. B. C.

10.

A. B.

Contents to all Volumes

Cyclopropenylium Salts

Synthesis Transformations Coordination Chemistry

Cyclobutanes

Synthesis Transformations Coordination Chemistry

Cyclobutenes

Synthesis Transformations Co ordination Chemistry

Cyclobutenediones

Synthesis Transformations Co ordination Chemistry

Cyclobutadienes

Synthesis Transformations

Author Index

Compound Index

Houben-Weyl

Volume E 17b

1. A.

3. 3.1.

3.1.1. 3.1.2. 3.1.3. 3.1.4. 3.2.

3.2.1. 3.2.1.1. 3.2.1.1.1. 3.2.1.1.2. 3.2.1.2. 3.2.1.3. 3.2.2. 4. 4.1.

4.1.1. 4.1.1.1. 4.1.1.2. 4.1.1.3. 4.1.1.4. 4.1.1.5. 4.1.1.6. 4.1.1.7. 4.1.2. 4.1.2.1. 4.1.2.2. 4.1.2.2.1. 4.1.2.2.2. 4.1.2.2.3. 4.1.2.2.4. 4.1.2.2.5. 4.1.2.2.6. 4.1.2.2.7. 4.1.2.2.8. 4.1.2.2.9. 4.1.2.2.10. 4.1.2.2.11.

Cyclopropanes Synthesis

Table of Contents

Volume E 17b

IX

Cyc1oadditions . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .. 967 Intramolecular Cyc1oadditions ................................... 967 (P. MARGARETHA)

Bicyc10[2.1.0]pentanes from l,4-Dienes . . . . . . . . . . . . . . . . . . . . . . . . . . .. 967 Prismanes from Dewar Benzenes . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .. 968 Quadricyc1anes from Norbornadienes . . . . . . . . . . . . . . . . . . . . . . . . . . . .. 968 Arene to Alkene Cyc1oadditions .................................. 970 Intermolecular Cyc1oadditions ................................... 973 (J.-L. RIPOLL)

Thermal Homo-Diels-Alder and Related Reactions ................. 973 Homo-Diels-Alder Reactions ([2ns + 2ns + 2ns] Cyc1oadditions) . . . . .. 973 Initiated by Heat or Pressure . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .. 973 Catalysis by Transition Metals . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .. 981 Homo-Diels-Alder Reactions Involving Extended n-Systems ......... 986 Homocheletropic Cyc1oadditions . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .. 987 Photochemical Arene-Alkene meta Cyc1oadditions . . . . . . . . . . . . . . . . .. 988 Ring Contraction .............................................. 995 From Four-Membered Rings. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .. 995 (1. SALAÜN)

By Elimination of a One-Atom Fragment. . . . . . . . . . . . . . . . . . . . . . . .. 995 Cyc1obutanones . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .. 995 Cyc1obutane-l,2-diones ......................................... 996 Cyc1obut-3-ene-l,2-diones ....................................... 997 Cyc1obutane-l,3-diones ......................................... 999 Oxacyc1obutylidenes ............................................ 1001 Thietane 1-0xides .............................................. 1002 Azetidinium Salts .............................................. 1004 By Rearrangement ............................................. 1007 Cyc10butyl Cation or Cyc10butylidene (Carbene) ................... 1007 Vicinally Difunctionalized Cyc10butanes ........................... 1020 2-Halo- and 2-Tosyloxycyc1obutanols ............................. 1020 Cyc1obutane-l,2-diols ........................................... 1024 1,2-Epoxycyc1obutanes .......................................... 1027 2-Hydroxycyc1obutanone Hydrate, Hemiacetals and Acetals .......... 1029 2-Halo- and 2-Tosyloxycyc1obutanones ............................ 1031 2-Bromocyc1obutanone Acetals .................................. 1037 Cyc1obutane-l,2-diones ......................................... 1038 2-Alkylidenecyc1obutanols ....................................... 1044 2-Halocyc1obutylamines ......................................... 1045 2-Diazocyc1obutanones ......................................... 1047 2-Diazoacetylcyc1obutanones .................................... 1049

x

4.1.2.2.12. 4.1.2.3. 4.2.

4.2.1. 4.2.1.1. 4.2.1.1.1. 4.2.1.1.2.

4.2.1.1.3. 4.2.1.1.4.

4.2.1.1.5. 4.2.1.1.6. 4.2.1.1.7. 4.2.1.1.8. 4.2.1.2. 4.2.1.2.1. 4.2.1.2.2. 4.2.2. 4.3.

4.3.1. 4.3.2. 4.3.3. 4.3.4. 4.3.5. 4.3.6. 4.3.7. 4.3.8. 4.3.9. 4.3.10. 4.3.11. 4.3.12. 4.3.13. 4.3.14. 4.3.15. 4.3.16. 4.3.17. 4.4. 4.4.1. 4.4.2. 4.4.3.

4.4.4. 4.4.5. 4.4.6. 4.4.7.

4.4.8.

4.4.9.

Table of Contents Houben-Weyl

Miscellaneous: Oxidative, Thermal and Photochemical Rearrangements 1051 I-Bromocyclobutanecarboxylic Acid and Ester ..................... 1054 From Five-Membered Rings ..................................... 1059 (R.J. BUSHBY)

By Elimination of a Two-Atom Fragment ......................... 1059 From 4,5-Dihydro-3H-pyrazoles ................................. 1059 Addition of Diazoalkanes to Acyclic Alkenes and Allenes ............ 1062 Additions of Diazoalkanes to Cyclic Alkenes and Heterocyclic Compounds ................................................... 1077 Intramolecular Additions of Diazoalkanes to Double Bonds ......... 1089 Cycloaddition Reactions of Dialkyl Azodicarboxylates and of 1,2,4-Triazole-3,5-diones ......................................... 1092 Addition Reactions to 3H- and 4H-Pyrazoles ...................... 1104 Nucleophilic Addition and Substitution Reactions of Hyrazine ....... 1109 Oxidation of 1,3-Diamines ...................................... 1113 Modification of the Structure of Other 4,5-Dihydropyrazoles ......... 1114 Other Precursors ............................................... 1121 y-Lactones .................................................... 1121 y-Sultines (1,2-0xathiolane 2-0xides) ............................. 1123 Rearrangements ................................................ 1124 From Six-Membered Rings ...................................... 1137 (1. SALAÜN)

Photochemistry of Benzene ...................................... 1137 Photoisomerization of 1,2-Dihydronaphthalenes .................... 1142 Photoisomerization of Cyclohexa-l,3-dienes ........................ 1144 Photoisomerization of Cyclohexa-l,4-dienes ........................ 1146 Photoisomerization of Cyclohex-2-enones .......................... 1150 Photoisomerization of Cross-Conjugated Cyclohexa-2,5-dienones ..... 1152 Photoisomerization of Cyclohex-3-enones .......................... 1156 Photoisomerization of Masked 1,2-Benzoquinones .................. 1160 Photoisomerization of Cyclohexenes .............................. 1161 Photolysis of 2,3-Diazabicyclo[2.2.1 ]hept-2-enes .................... 1163 Electrolysis of Cyclohexa-l ,4-dienes ............................... 1167 Ring Contraction of 2-Halocyclohexanone Enamines ................ 1168 Ring Contraction of 4-Halo- and 4-Tosyloxycyclohexanone Enolates .. 1176 Ring Contraction of Cyclohex-3-enones by Secondary Amines ........ 1177 Electrophilic Ring Contraction of Cyclohexa-l ,4-dienes .............. 1178 Ring Contraction Involving 3-Methylenecyclohexyl Cations .......... 1185 Miscellaneous ................................................. 1187 From Larger Rings ............................................. 1199 Cycloheptatriene/Norcaradiene Valence Isomerization ............... 1199 Cyclohepta-l,3- and -l,4-diene Isomerization ....................... 1201 Ring Contraction of 2-Halo- and 2-Sulfoniocycloheptanone Enamines ..................................................... 1212 Ring Contraction of Cyclohept-3-enol Derivatives .................. 1215 Ring Contraction of a-Halo- and a,a'-Dihalocycloheptanones ........ 1216 Photoisomerization of Cyclooctatetraenes ......................... 1218 Ring Contraction of Cyclooct-3-enol Esters and Cyclo-octa -1 ,4-dienes ................................................. 1221 Ring Contraction of Cycloocta-l ,4-diene Monoepoxide and in situ Generated Cyclooctanylidenes ................................... 1222 Reductive Cyclization of 1,5-Dihalobicyclo[3.2.1]octanes and 1,5-Dihalo bicyclo[3. 3.1 ]nonanes .................................. 1224

Volume E 17b

4.4.10.

4.4.11. 4.4.12. 4.4.13. 4.4.14. 4.4.15.

5. 5.1.

5.1.1. 5.1.2. 5.1.3. 5.1.4.

5.2. 5.2.1.

5.2.1.1. 5.2.1.1.1. 5.2.1.1.1.1. 5.2.1.1.1.2. 5.2.1.1.1.3. 5.2.1.1.1.4. 5.2.1.1.1.5. 5.2.1.1.1.6. 5.2.1.1.1.7. 5.2.1.1.1.8. 5.2.1.1.1.9. 5.2.1.1.1.10. 5.2.1.1.1.11. 5.2.1.1.1.12. 5.2.1.1.1.13. 5.2.1.1.2. 5.2.1.1.3. 5.2.1.1.4. 5.2.1.1.5. 5.2.1.1.6. 5.2.1.1.7. 5.2.1.1.8. 5.2.1.1.9. 5.2.1.1.10. 5.2.1.1.10.1. 5.2.1.1.1 0.2. 5.2.1.1.10.3. 5.2.1.1.1 0.4. 5.2.1.1.11. 5.2.1.1.11.1. 5.2.1.1.11.2. 5.2.1.1.11.3. 5.2.1.1.11.4. 5.2.1.1.12.

Table of Contents XI

Transannular Cyclization of Eight- and Nine-Membered y-Epoxy Sulfones ...................................................... 1225 Photoisomerization of Cyclononatetraene .......................... 1227 Cyclization of Cyclonona-l,4,7-triyne ............................. 1227 Photoisomerization of Cyclonona-l,2-diene ........................ 1227 Alder-Rickert Cleavage of 1,6-Methano[12]annulene Adducts ........ 1229 Electrophilic Ring Contraction of Humulene and Related Epoxides ...................................................... 1229 By Transformation of Other Cyclopropanes ........................ 1235 With Cleavage of a Cyclopropyl-Carbon Bond ..................... 1235 (A.J. H. KLUNDER and B. ZWANENBURG) Decarbonylation or Decarboxylation .............................. 1235 Halodecarboxylation ........................................... 1239 Rearrangement ................................................ 1242 Formation of Cyclopropylmethyl Derivatives from Bicyclo[1.1.0]butanes ........................................... 1249 Without Cleavage of a Cyclopropyl-Carbon Bond .................. 1255 Substitution Reactions .......................................... 1255 (L. K. SYDNES) Substitution of One Group Attached to the Ring ................... 1255 Formation of a C-H or C-D Bond ............................... 1255 Cleavage of a C-H Bond ........................................ 1255 Cleavage of aC-Li Bond ....................................... 1255 Cleavage of aC-Co Bond ....................................... 1256 Cleavage of aC-Hg Bond ...................................... 1256 Cleavage of a C-B Bond ........................................ 1256 Cleavage of aC-HaI Bond ...................................... 1256 Cleavage of a C-O Bond ........................................ 1276 Cleavage of a C-S Bond ........................................ 1277 Cleavage of aC-Se Bond ....................................... 1279 Cleavage of a C-N Bond ........................................ 1279 Cleavage of a C-P Bond ........................................ 1280 Cleavage of aC-Si Bond ........................................ 1282 Cleavage of aC-Sn Bond ....................................... 1283 Formation of aC-Li Bond ...................................... 1284 Formation of aC-Mg Bond ..................................... 1285 Formation of a C-Ti Bond ...................................... 1285 Formation of aC-Fe Bond ...................................... 1286 Formation of aC-Co Bond ..................................... 1287 Formation of aC-Rh Bond ..................................... 1287 Formation of aC-Hg Bond ..................................... 1287 Formation of a C-B Bond ...................................... 1288 Formation of aC-HaI Bond ..................................... 1289 Formation of a C-F Bond ...................................... 1289 Formation of aC-Cl Bond ...................................... 1289 Formation of a C-Br Bond ...................................... 1292 Formation of a C-I Bond ....................................... 1296 Formation of a C-O Bond ...................................... 1297 Cyclopropanols ................................................ 1297 Cyclopropyl Ethers ............................................. 1299 Cyclopropyl Esters ............................................. 1305 Oxasp~opentanes .............................................. 1308 Formation of a C-S Bond ....................................... 1310

XII

5.2.1.1.12.1. 5.2.1.1.12.2. 5.2.1.1.12.3. 5.2.1.1.13. 5.2.1.1.14. 5.2.1.1.15. 5.2.1.1.16. 5.2.1.1.17 . 5.2.1.1.17 .1. 5.2.1.1.17.2. 5.2.1.1.17.3. 5.2.1.1.17.4. 5.2.1.1.17 .5. 5.2.1.1.17.6. 5.2.1.1.17.7. 5.2.1.1.17.8. 5.2.1.1.17 .9. 5.2.1.1.17.10. 5.2.1.1.17.11. 5.2.1.1.18. 5.2.1.1.18.1. 5.2.1.1.18.2. 5.2.1.1.18.3. 5.2.1.1.19. 5.2.1.2.

5.2.1.2.1. 5.2.1.2.2. 5.2.1.2.3. 5.2.1.2.4. 5.2.1.2.5. 5.2.1.2.6. 5.2.1.2.7. 5.2.1.2.8. 5.2.1.2.9. 5.2.1.2.10. 5.2.1.2.11. 5.2.1.2.12. 5.2.1.2.13. 5.2.1.2.14. 5.2.1.2.15. 5.2.1.2.15.1. 5.2.1.2.15.2. 5.2.1.2.16. 5.2.1.2.17. 5.2.1.3.

5.2.1.3.1. 5.2.1.3.2. 5.2.1.3.3. 5.2.1.3.4. 5.2.1.3.5. 5.2.1.3.6.

Table of Contents Houben-Weyl

Substitution of a Hydrogen Atom ................................ 1310 Substitution of a Halogen Atom ................................. 1311 Substitution of Other Groups .................................... 1314 Formation of aC-Se Bond ...................................... 1315 Formation of a C-N Bond ...................................... 1316 Formation of a C-P Bond ....................................... 1320 Formation of a C-As Bond ..................................... 1322 Formation of a C-C Bond ...................................... 1323 Cleavage of a C-H Bond ........................................ 1323 Cleavage of aC-Hai Bond ...................................... 1333 Cleavage of a C-Ti Bond ....................................... 1356 Cleavage of aC-Hg Bond ....................................... 1357 Cleavage of aC-Si Bond ........................................ 1358 Cleavage of aC-Sn Bond ....................................... 1361 Cleavage of a C-N Bond ........................................ 1362 Cleavage of a C-P Bond ........................................ 1363 Cleavage of a c-o Bond ........................................ 1364 Cleavage of a C-S Bond ........................................ 1368 Cleavage of aC-Se Bond ....................................... 1372 Formation of aC-Si Bond ...................................... 1375 Substitution of a C-H Bond ..................................... 1375 Substitution of aC-Hai Bond ................................... 1378 Substitution of Other Bonds ..................................... 1380 Formation of aC-Sn Bond ...................................... 1382 Substitution of Two Groups Attached to the Same Carbon Atom in the Ring .................................................... 1383 Formation of Two C-H and C-D Bonds .......................... 1383 Formation of One C-H and One C-B Bond ....................... 1385 Formation of One C-H and One C-O Bond ....................... 1386 Formation of One C-H and One C-S Bond ....................... 1387 Formation of One C-H and One C-P Bond ....................... 1388 Formation of One C-H and One C-C Bond ....................... 1389 Formation of One C-H and One C-Si Bond ....................... 1394 Formation of Two C-Hal Bonds ................................. 1394 Formation of One C-Hal and One C-C Bond ..................... 1395 Formation of Two C-O Bonds ................................... 1395 Formation of One C-O and One C-C Bond ....................... 1396 Formation of Two C-S Bonds ................................... 1398 Formation of Two C-Se Bonds .................................. 1400 Formation of Two C-P Bonds ................................... 1401 Formation of Two C-C Bonds ................................... 1401 1,1-Dialky1cyc1opropanes ........................................ 1401 Alkylidenecyc1opropanes ........................................ 1405 Formation of One C-C and One C-B Bond ....................... 1407 Formation of Two C-Si Bonds ................................... 1407 Substitution of Two Groups Attached to Different Carbon Atoms in the Ring .................................................... 1408 Formation of Two C-D Bonds ................................... 1408 Formation of One C-H and One C-O Bond ....................... 1408 Formation of One C-H and One C-S Bond ....................... 1409 Formation of One C-H and One C-Se Bond ...................... 1410 Formation of One C-H and One C-C Bond ....................... 1411 Formation of Two C-C Bonds ................................... 1412

Volume E 17b

5.2.1.3.7. 5.2.2.

5.2.2.1. 5.2.2.1.1. 5.2.2.1.1.1. 5.2.2.1.1.2. 5.2.2.1.1.3. 5.2.2.1.1.4. 5.2.2.1.2. 5.2.2.1.2.1. 5.2.2.1.2.2. 5.2.2.1.2.3. 5.2.2.1.2.4. 5.2.2.1.2.5. 5.2.2.1.3. 5.2.2.1.3.1. 5.2.2.1.3.2. 5.2.2.2. 5.2.2.2.1. 5.2.2.2.2. 5.2.2.2.3. 5.2.2.3. 5.2.2.3.1. 5.2.2.3.2. 5.2.2.4. 5.2.2.5. 5.2.2.5.1. 5.2.2.5.2. 5.2.2.5.3. 5.2.2.6. 5.2.2.6.1. 5.2.2.6.2. 5.2.2.7. 5.2.2.7.1. 5.2.2.7.1.1. 5.2.2.7.1.2. 5.2.2.7.1.3. 5.2.2.7.2. 5.2.2.7.3. 5.2.2.7.3.1. 5.2.2.7.3.2. 5.2.2.7.3.3. 5.2.2.7.4. 5.2.2.7.5. 5.2.2.7.6. 5.2.3. 5.2.3.1.

5.2.3.1.1. 5.2.3.1.1.1. 5.2.3.1.1.2. 5.2.3.1.1.3.

Table of Contents XIII

Formation of Two C-Si Bonds ................................... 1414 Elimination Reactions .......................................... 1433 (l. GOLDSCHMIDT and J.L. WOLK) 1,2-Eliminations of Hydrogen Halides ............................. 1433 Monodehydrohalogenations ..................................... 1433 Methylenecyclopropanes ........................................ 1433 Alkylidene- and Alkenylidenecyclopropanes ........................ 1443 Alkenykyclopropanes ........................................... 1448 Alkynykyclopropanes .......................................... 1450 Didehydrohalogenations ........................................ 1451 Bis(methylene)triangulanes ...................................... 1451 Dialkylidene- and Dialkenykyclopropanes ......................... 1453 Alkenyl(alkylidene)cyclopropanes ................................. 1455 6-Methylenebicyclo[3.1.0]hex-2-enes ............................... 1458 Cycloproparenes ............................................... 1459 Dehydrohalogenation-Addition Reactions ......................... 1471 From 1,1-Dihalocyclopropanes ................................... 1471 From 1,2-Dihalo-1-methykyclopropanes .......................... 1475 Dehydrations .................................................. 1476 Acid-Catalyzed Dehydration ..................................... 1476 Dehydration of ß-Hydroxy Silanes ............................... 1476 Dehydration of ß-Hydroxy Sulfanyl- and Selanykyclopropanes ....... 1479 Eliminations Involving Other Oxygen Fragmentation ............... 1482 Elimination of Carboxylate ...................................... 1482 Elimination of Sulfonates ....................................... 1483 Eliminations Involving Sulfur and Selenium Fragmentation .......... 1484 Eliminations Involving Nitrogen Fragmentation .................... 1487 Elimination of Amines .......................................... 1487 Elimination of Nitrous Acid ..................................... 1488 Elimination of Molecular Nitrogen ............................... 1488 Eliminations Involving Two Ca rb on-Atom Fragmentations .......... 1489 Retro-Diels-Alder Reaction ..................................... 1489 Decarboxylation ............................................... 1490 Eliminations Involving Two Hetero-Atom Fragmentations ........... 1490 Dehalogenation ................................................ 1490 1,2-Dehalogenation ............................................. 1490 1,I-Debromination ............................................. 1492 Debromination with Sigmatropic Rearrangement ................... 1493 Dehydroxysilylation (Peterson Olefination) ........................ 1493 Dehydroxysulfuration and Dehydroxyselenation .................... 1497 Alkylidenecyclopropanes ........................................ 1497 Alkenyl(selanyl)cyclopropanes and Alkenyl(silyl)cyclopropanes ....... 1498 (Sulfanylethenyl)- and (Selanylethenyl)cyclopropanes ................ 1499 Dehydroxyphosphoration ....................................... 1501 Desulfonosilylation ............................................. 1501 Debromostannation ............................................ 1502 By Addition Reactions to Exocyclic Double Bonds ................. 1507 C-C Double Bonds Without Functional Groups ................... 1507 (S. VON ANGERER)

Additions ..................................................... 1507 Halogens ..................................................... 1507 Hydrohalic Acids .............................................. 1508 Perhaloalkanes ................................................. 1509

XIV

5.2.3.1.1.4. 5.2.3.1.1.5. 5.2.3.1.1.6. 5.2.3.1.1. 7. 5.2.3.1.1.8. 5.2.3.1.2. 5.2.3.1.2.1. 5.2.3.1.2.2. 5.2.3.1.2.3. 5.2.3.1.2.4. 5.2.3.1.2.5. 5.2.3.1.3. 5.2.3.1.3.1. 5.2.3.1.3.2. 5.2.3.2.

5.2.3.2.1.

5.2.3.2.1.1. 5.2.3.2.1.2. 5.2.3.2.2. 5.2.3.2.2.1. 5.2.3.2.2.2. 5.2.3.3.

5.2.3.3.1.

5.2.3.3.2.

5.2.3.3.3.

5.2.3.3.4.

5.2.3.3.4.1. 5.2.3.3.4.2. 5.2.3.3.4.3. 5.2.3.3.4.4. 5.2.3.3.4.5. 5.2.3.3.4.6. 5.2.3.3.5. 5.2.3.4.

5.2.3.4.1. 5.2.3.4.2. 5.2.3.5. 5.2.3.5.1.

5.2.3.5.2. 5.2.3.5.2.1 5.2.3.5.2.2. 5.2.3.5.3. 5.2.3.5.4. 5.2.3.5.5.

Table of Contents Houben-Weyl

N ucleophiles .................................................. 1509 Pseudohalides ................................................. 1511 Polarized Double Bonds ........................................ 1511 Transition-Metal Complexes ..................................... 1512 HydroborationjOxidation ....................................... 1513 Cycloadditions ................................................. 1514 [2+1] Cycloadditions ........................................... 1514 [2 + 2] Cycloadditions (Codimerizations) ........................... 1519 [2 + 3] Cycloadditions ........................................... 1526 [2+4] Cycloadditions ........................................... 1530 [4 + 2] Cycloadditions ........................................... 1533 Oligomerization ................................................ 1536 Dimerization .................................................. 1536 Trimerization .................................................. 1541 C-C Double Bonds with Functional Groups ....................... 1545 (A. STOLLE) Methylenecyclopropanes Bearing Electron-Withdrawing Substituents ................................................... 1545 Nucleophilic Addition Reactions ................................. 1545 Cycloaddition Reactions ........................................ 1555 Methylenecyclopropanes Bearing Electron-Donating Substituents ..... 1567 Electrophilic Addition Reactions ................................. 1567 Cycloaddition Reactions ........................................ 1570 C-N Double Bonds in Cyclopropaniminium Salts or Intermediates ... 1577 (J. SEIBEL and E. VILSMAIER) Generation, Stability, and Characterization of Free Cyclopro-paniminium Ions ............................................... 1577 Generation of Cyclopropaniminium Ions in Nucleophilic Substitution of Cyclopropylamine Derivatives ...................... 1578 Stereochemistry of Nucleophilic Substitution of Annulated Cyclopropylamine Derivatives ................................... 1578 Nucleophilic Substitution via Cyclopropaniminium Ions from Cyclopropylamine Precursors .................................... 1580 Carbon Nucleophiles ........................................... 1580 Nitrogen Nucleophiles .......................................... 1590 Oxygen N ucleophiles ........................................... 1594 Sulfur N ucleophiles ............................................ 1596 Hydrogen Nucleophiles ......................................... 1598 Halide as N ucleophile .......................................... 1600 Cyclopropaniminium Ions from Methyleneaziridine Precursors ....... 1600 C-N Double Bonds ............................................ 1603 (N. DE KIMPE) Addition of A1cohols ........................................... 1603 Addition of Cyanide ............................................ 1609 C-O Double Bonds ............................................ 1612 Addition of A1cohols, Alkoxides, Water and Other Oxygen N ucleophiles .................................................. 1620 Addition of Amines and Derivatives of Amines .................... 1626 Primary Amines and Related Reagents ............................ 1626 Secondary Amines and Related Reagents .......................... 1634 Addition of Azide .............................................. 1636 Addition of Hydrogen Sulfide and Thiols .......................... 1638 Addition of Hydride ............................................ 1640