Organic Reactions, Volume 109 E-Book
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- Herausgeber: John Wiley & Sons
- Kategorie: Wissenschaft und neue Technologien
- Serie: Organic Reactions
- Sprache: Englisch
The 109th volume in this series for organic chemists in academia and industry presents critical discussions of widely used organic reactions or particular steps of a reaction. The material is treated from a preparative viewpoint, with emphasis on limitations, interfering influences, effects of structure and the selection of experimental techniques. The work includes tables that contain all possible examples of the reaction under consideration. Detailed procedures illustrate the significant modifications of each method.
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Table of Contents
Cover
Title Page
Copyright
Introduction to the Series by Roger Adams, 1942
INTRODUCTION TO THE SERIES BY SCOTT E. DENMARK, 2008
PREFACE TO VOLUME 109
CHAPTER 1: EXTRUSION REACTIONS AFFORDING AROMATIC SYSTEMS, DIENES AND POLYENES
ACKNOWLEDGMENTS
INTRODUCTION
MECHANISM AND STEREOCHEMISTRY
SCOPE AND LIMITATIONS
APPLICATIONS TO SYNTHESIS
COMPARISON WITH OTHER METHODS
EXPERIMENTAL CONDITIONS
EXPERIMENTAL PROCEDURES
TABULAR SURVEY
REFERENCES
SUPPLEMENTAL REFERENCES
CUMULATIVE CHAPTER TITLES BY VOLUME
AUTHOR INDEX, VOLUMES 1‐109
CHAPTER AND TOPIC INDEX, VOLUMES 1‐109
END USER LICENSE AGREEMENT
List of Illustrations
Chapter 1
Scheme 1
Scheme 2
Scheme 3
Scheme 4
Scheme 5
Scheme 6
Scheme 7
Scheme 8
Scheme 9
Scheme 10
Scheme 11
Scheme 12
Scheme 13
Scheme 14
Scheme 15
Figure 1 Polysubstituted sulfone and sulfoxide extrusion substrates.
Scheme 16
Scheme 17
Scheme 18
Scheme 19
Scheme 20
Figure 2 Bicylic ketones as substrates for decarbonylation.
Scheme 21
Scheme 22
Scheme 23
Scheme 24
Scheme 25
Scheme 26
Scheme 27
Scheme 28
Scheme 29 The generation of several strained cyclic alkynes is demonstrated...
Scheme 30
Scheme 31
Scheme 32
Scheme 33
Scheme 34
Scheme 35
Scheme 36
Scheme 37
Figure 3 Precursors for nanotube synthesis.
Scheme 38
Scheme 39
Scheme 40
Scheme 41
Scheme 42
Scheme 43
Scheme 44
Scheme 45
Figure 4 Some polyacetylenic cores for dendrimer formation.
Scheme 46
Scheme 47
Scheme 48
Scheme 49
Scheme 50
Scheme 51
Scheme 52
Scheme 53
Scheme 54
Scheme 55
Scheme 56
Scheme 57
Scheme 58
Scheme 59
Figure 5 Some ring‐fused cyclopentadienones.
Scheme 60
Scheme 61
Scheme 62
Scheme 63
Scheme 64
Scheme 65
Scheme 66
Scheme 67
Scheme 68
Scheme 69
Figure 6 Structure of heptacene.
Scheme 70
Scheme 71
Scheme 72
Scheme 73
Scheme 74
Scheme 75 The 1,3‐dipolar cycloaddition of nitrone
41
with phenylisocyanate...
Scheme 76
Scheme 77
Scheme 78
Scheme 79
Scheme 80
Scheme 81
Scheme 82
Scheme 83
Scheme 84
Scheme 85 The thermal cycloaddition of cyclopentadienones with vinylidene c...
Scheme 86
Scheme 87
Scheme 88
Scheme 89
Scheme 90
Scheme 91
Scheme 92
Scheme 93
Scheme 94
Scheme 95
Scheme 96
Scheme 97
Scheme 98
Scheme 99
Scheme 100
Scheme 101
Scheme 102
Scheme 103
Scheme 104
Scheme 105
Scheme 106
Scheme 107
Scheme 108
Scheme 109
Scheme 110
Scheme 111
Scheme 112
Scheme 113
Scheme 114
Scheme 115
Scheme 116
Scheme 117
Scheme 118
Scheme 119
Scheme 120
Scheme 121
Scheme 122
Scheme 123
Scheme 124 Thiophene dioxide, which is generated in situ, undergoes cycload...
Scheme 125
Scheme 126
Scheme 127
Scheme 128
Scheme 129
Scheme 130
Scheme 131
Scheme 132
Scheme 133
Scheme 134
Scheme 135
Scheme 136
Scheme 137
Scheme 138
Scheme 139
Scheme 140
Scheme 141
Scheme 142
Scheme 143
Scheme 144
Scheme 145
Scheme 146
Scheme 147
Scheme 148
Scheme 149
Scheme 150
Scheme 151
Scheme 152
Scheme 153
Scheme 154
Scheme 155
Scheme 156
Scheme 157
Scheme 158
Scheme 159
Scheme 160
Scheme 161
Scheme 162
Scheme 163
Scheme 164
Scheme 165
Scheme 166
Scheme 167
Scheme 168
Scheme 169
Scheme 170
Scheme 171
Scheme 172
Figure 7 Stable thiophene‐1‐oxides.
Scheme 173
Scheme 174
Scheme 175
Scheme 176
Scheme 177
Scheme 178
Scheme 179
Scheme 180
Scheme 181
Scheme 182
Scheme 183
Scheme 184
Scheme 185
Scheme 186
Scheme 187
Scheme 188
Scheme 189
Scheme 190
Scheme 191
Scheme 192
Scheme 193
Scheme 194
Scheme 195
Scheme 196
Scheme 197
Scheme 198
Scheme 199
Scheme 200
Scheme 201
Scheme 202
Scheme 203
Scheme 204
Scheme 205
Scheme 206
Scheme 207
Scheme 208
Figure 8 Isobenzofurans and analogues.
Scheme 209
Scheme 210
Scheme 211
Scheme 212
Scheme 213
Scheme 214
Scheme 215
Scheme 216
Scheme 217
Scheme 218
Scheme 219
Scheme 220
Scheme 221
Scheme 222
Scheme 223
Scheme 224
Scheme 225
Scheme 226
Scheme 227
Scheme 228
Scheme 229
Scheme 230
Scheme 231
Scheme 232
Scheme 233
Scheme 234
Scheme 235
Scheme 236
Scheme 237
Scheme 238
Scheme 239
Scheme 240
Scheme 241
Scheme 242
Scheme 243
Scheme 244
Scheme 245
Scheme 246
Scheme 247
Scheme 248
Scheme 249
Scheme 250
Scheme 251
Scheme 252
Scheme 253
Scheme 254
Scheme 255
Scheme 256
Scheme 257
Scheme 258
Scheme 259
Scheme 260
Scheme 261
Scheme 262
Scheme 263
Scheme 264
Scheme 265
Scheme 266
Scheme 267
Scheme 268
Scheme 269
Scheme 270
Scheme 271
Scheme 272
Scheme 273
Scheme 274
Scheme 275
Scheme 276
Scheme 277
Scheme 278
Scheme 279
Scheme 280
Scheme 281
Scheme 282
Scheme 283
Scheme 284
Scheme 285
Scheme 286
Scheme 287
Scheme 288
Scheme 289
Scheme 290
Scheme 291
Scheme 292
Scheme 293
Scheme 294
Scheme 295
Scheme 296
Scheme 297
Scheme 298
Scheme 299
Scheme 300
Scheme 301
Scheme 302
Scheme 303
Scheme 304
Scheme 305
Scheme 306
Scheme 307
Scheme 308
Scheme 309
Scheme 310
Scheme 311
Scheme 312
Scheme 313
Scheme 314
Scheme 315
Scheme 316
Scheme 317
Scheme 318
Scheme 319
Scheme 320
Scheme 321
Scheme 322
Scheme 323
Scheme 324
Scheme 325
Scheme 326
Scheme 327
Scheme 328
Scheme 329
Scheme 330
Scheme 331
Scheme 332
Scheme 333
Scheme 334
Figure 9 Sultines and related sulfolenes.
Scheme 335
Scheme 336
Scheme 337
Scheme 338
Scheme 339
Scheme 340
Scheme 341
Scheme 342
Scheme 343
Scheme 344
Scheme 345
Figure 10 Some pheromones and pheromone analogues synthesized by sulfolene a...
Figure 11 Insecticidal compounds prepared using sulfolene alkylation‐sulfur ...
Scheme 346
Scheme 347
Scheme 348
Scheme 349
Scheme 350
Scheme 351
Scheme 352
Scheme 353
Scheme 354
Scheme 355
Scheme 356
Scheme 357
Scheme 358
Scheme 359
Scheme 360
Scheme 361
Guide
Cover Page
Table of Contents
Title Page
Copyright
Introduction to the Series by Roger Adams, 1942
INTRODUCTION TO THE SERIES BY SCOTT E. DENMARK, 2008
PREFACE TO VOLUME 109
Begin Reading
CUMULATIVE CHAPTER TITLES BY VOLUME
AUTHOR INDEX, VOLUMES 1‐109
CHAPTER AND TOPIC INDEX, VOLUMES 1‐109
WILEY END USER LICENSE AGREEMENT
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FORMER MEMBERS OF THE BOARD OF EDITORS AND DIRECTORS
JEFFREY
AUBÉ
LAURA
KIESSLING
JOHN
E.
BALDWIN
MARISA
C.
KOZLOWSKI
PETER
BEAK
STEVEN
V.
LEY
DALE
L.
BOGER
JAMES
A.
MARSHALL
ANDRÉ
B.
CHARETTE
MICHAEL
J.
MARTINELLI
ENGELBERT
CIGANEK
STUART
W.
MC
COMBIE
DENNIS
CURRAN
SCOTT
J.
MILLER
SAMUEL
DANISHEFSKY
JOHN
MONTGOMERY
HUW
M. L.
DAVIES
LARRY
E.
OVERMAN
SCOTT
E.
DENMARK
T. V.
RAJANBABU
VICTOR
FARINA
JAMES
H.
RIGBY
PAUL
FELDMAN
WILLIAM
R.
ROUSH
JOHN
FRIED
TOMISLAV
ROVIS
JACQUELYN
GERVAY
‐
HAGUE
SCOTT
D.
RYCHNOVSKY
STEPHEN
HANESSIAN
MARTIN
SEMMELHACK
LOUIS
HEGEDUS
CHARLES
SIH
PAUL
J.
HERGENROTHER
AMOS
B.
SMITH
, III
DONNA
M.
HURYN
BARRY
M.
TROST
JEFFREY
S.
JOHNSON
PETER
WIPF
ROBERT
C.
KELLY
FORMER MEMBERS OF THE BOARD NOW DECEASED
ROGER
ADAMS
HERBERT
O.
HOUSE
HOMER
ADKINS
JOHN
R.
JOHNSON
WERNER
E.
BACHMANN
ROBERT
M.
JOYCE
ROBERT
BITTMAN
ANDREW
S.
KENDE
A. H.
BLATT
WILLY
LEIMGRUBER
VIRGIL
BOEKELHEIDE
FRANK
C.
MC
GREW
GEORGE
A.
BOSWELL
,
JR
.
BLAINE
C.
MC
KUSICK
THEODORE
L.
CAIRNS
JERROLD
MEINWALD
ARTHUR
C.
COPE
CARL
NIEMANN
DONALD
J.
CRAM
LEO
A.
PAQUETTE
DAVID
Y.
CURTIN
GARY
H.
POSNER
WILLIAM
G.
DAUBEN
HANS
J.
REICH
LOUIS
F.
FIESER
HAROLD
R.
SNYDER
HEINZ
W.
GSCHWEND
MILÁN
USKOKOVIC
RICHARD
F.
HECK
BORIS
WEINSTEIN
RALPH
F.
HIRSCHMANN
JAMES
D.
WHITE
Organic Reactions
VOLUME 109
EDITORIAL BOARD
P. ANDREWEVANS, Editor‐in‐Chief
STEVEN M. WEINREB, Executive Editor
DAVID
B.
BERKOWITZ
DAVID
A.
NAGIB
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R.
BLAKEMORE
ALBERT
PADWA
JIN
K.
CHA
JENNIFER
M.
SCHOMAKER
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L.
GRANGE
KEVIN
H.
SHAUGHNESSY
DENNIS
G.
HALL
STEVEN
D.
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B.
JOHNSON
CHRISTOPHER
D.
VANDERWAL
JEFFREY
N.
JOHNSTON
MARY
P.
WATSON
STEFAN
LUTZ
BARRY B. SNIDER, Secretary
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ASSOCIATE EDITORS
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LYNNJAMESGUZIEC
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ISBN: 978‐1‐119‐83208‐9
Introduction to the Series by Roger Adams, 1942
In the course of nearly every program of research in organic chemistry, the investigator finds it necessary to use several of the better‐known synthetic reactions. To discover the optimum conditions for the application of even the most familiar one to a compound not previously subjected to the reaction often requires an extensive search of the literature; even then a series of experiments may be necessary. When the results of the investigation are published, the synthesis, which may have required months of work, is usually described without comment. The background of knowledge and experience gained in the literature search and experimentation is thus lost to those who subsequently have occasion to apply the general method. The student of preparative organic chemistry faces similar difficulties. The textbooks and laboratory manuals furnish numerous examples of the application of various syntheses, but only rarely do they convey an accurate conception of the scope and usefulness of the processes.
For many years American organic chemists have discussed these problems. The plan of compiling critical discussions of the more important reactions thus was evolved. The volumes of Organic Reactions are collections of chapters each devoted to a single reaction, or a definite phase of a reaction, of wide applicability. The authors have had experience with the processes surveyed. The subjects are presented from the preparative viewpoint, and particular attention is given to limitations, interfering influences, effects of structure, and the selection of experimental techniques. Each chapter includes several detailed procedures illustrating the significant modifications of the method. Most of these procedures have been found satisfactory by the author or one of the editors, but unlike those in Organic Syntheses, they have not been subjected to careful testing in two or more laboratories. Each chapter contains tables that include all the examples of the reaction under consideration that the author has been able to find. It is inevitable, however, that in the search of the literature some examples will be missed, especially when the reaction is used as one step in an extended synthesis. Nevertheless, the investigator will be able to use the tables and their accompanying bibliographies in place of most or all of the literature search so often required. Because of the systematic arrangement of the material in the chapters and the entries in the tables, users of the books will be able to find information desired by reference to the table of contents of the appropriate chapter. In the interest of economy, the entries in the indices have been kept to a minimum, and, in particular, the compounds listed in the tables are not repeated in the indices.
The success of this publication, which will appear periodically, depends upon the cooperation of organic chemists and their willingness to devote time and effort to the preparation of the chapters. They have manifested their interest already by the almost unanimous acceptance of invitations to contribute to the work. The editors will welcome their continued interest and their suggestions for improvements in Organic Reactions.
INTRODUCTION TO THE SERIES BY SCOTT E. DENMARK, 2008
In the intervening years since “The Chief” wrote this introduction to the second of his publishing creations, much in the world of chemistry has changed. In particular, the last decade has witnessed a revolution in the generation, dissemination, and availability of the chemical literature with the advent of electronic publication and abstracting services. Although the exponential growth in the chemical literature was one of the motivations for the creation of Organic Reactions, Adams could never have anticipated the impact of electronic access to the literature. Yet, as often happens with visionary advances, the value of this critical resource is now even greater than at its inception.
From 1942 to the 1980's the challenge that Organic Reactions successfully addressed was the difficulty in compiling an authoritative summary of a preparatively useful organic reaction from the primary literature. Practitioners interested in executing such a reaction (or simply learning about the features, advantages, and limitations of this process) would have a valuable resource to guide their experimentation. As abstracting services, in particular Chemical Abstracts and later Beilstein, entered the electronic age, the challenge for the practitioner was no longer to locate all of the literature on the subject. However, Organic Reactions chapters are much more than a surfeit of primary references; they constitute a distillation of this avalanche of information into the knowledge needed to correctly implement a reaction. It is in this capacity, namely to provide focused, scholarly, and comprehensive overviews of a given transformation, that Organic Reactions takes on even greater significance for the practice of chemical experimentation in the 21st century.
Adams' description of the content of the intended chapters is still remarkably relevant today. The development of new chemical reactions over the past decades has greatly accelerated and has embraced more sophisticated reagents derived from elements representing all reaches of the Periodic Table. Accordingly, the successful implementation of these transformations requires more stringent adherence to important experimental details and conditions. The suitability of a given reaction for an unknown application is best judged from the informed vantage point provided by precedent and guidelines offered by a knowledgeable author.
As Adams clearly understood, the ultimate success of the enterprise depends on the willingness of organic chemists to devote their time and efforts to the preparation of chapters. The fact that, at the dawn of the 21st century, the series continues to thrive is fitting testimony to those chemists whose contributions serve as the foundation of this edifice. Chemists who are considering the preparation of a manuscript for submission to Organic Reactions are urged to contact the Editor‐in‐Chief.
PREFACE TO VOLUME 109
The wings of transformation are born of patience and struggle.
Janet S. Dickens
The ability to control chemical reactivity and selectivity represents the very essence of modern synthetic organic chemistry, albeit these goals often pose complex challenges for chemists engaged in discovering new chemical reactions. For instance, highly reactive reagents often demonstrate low selectivity, limit substrate scope, and lead to competing side reactions. Consequently, many reactive intermediates are best generated from less reactive precursors under mild and often catalytic conditions to mitigate some of these detrimental issues. The ability to “mask” and “trigger” chemical reactivity provides a measurable strategic advantage that often underpins the evolution of a basic synthetic method into a sophisticated and practical process with fewer limitations. Hence, the challenges encountered in developing such a transformation are indeed “born of patience and struggle,” which may disguise the extensive experimentation required to enable the “metamorphosis” of a simple hypothesis into a robust chemical transformation.
The Organic Reactions series provides an enduring narrative that showcases the so‐called “life‐cycle” of these developments, which can be ascribed to the unique blueprint provided by Roger Adams at the outset of this venerable series in 1942. As part of this vision, the chapters are written by recognized experts in the field in a consistent and unified format to disseminate critical features of the transformation that enables the practicing synthetic organic chemist to gain the in‐depth understanding and insight necessary to utilize the reaction successfully. For example, the chapters dissect crucial elements of a process within the context of the reaction mechanism and stereochemistry, scope and limitations, applications to synthesis, a comparison with other methods, and critical experimental details and procedures. For this reason, Organic Reactions chapters provide unparalleled insights into the various underpinnings of an important chemical reaction that would be challenging to assimilate, even with modern computerized search engines.
This single‐chapter volume by Frank S. Guziec, Jr. and Lynn James Guziec provides a comprehensive treatise on extrusion reactions, which involve the loss of a small, stable inorganic molecule, such as carbon dioxide and nitrogen, or an atom, such as sulfur, from an organic precursor. Hence, the chapter deals with the notion of “unmasking” chemical reactivity to access arenes, dihydroarenes, heteroarenes, dienes, and polyenes and other challenging targets. The chapter provides an update on the extrusion of carbon dioxide and nitrogen in retro‐Diels‐Alder reactions (Volumes 52 and 53); however, the related Ramberg‐Bäcklund reaction with the extrusion of sulfur dioxide (Volumes 25 and 62) and the Eschenmoser‐type ring‐contraction‐extrusion reaction are not included. The introduction briefly defines extrusion and cheletropic processes, which are formally a type of pericyclic reaction that proceeds via a cyclic transition state with reorganization of σ‐ and π‐bonds. The mechanistic aspects of these reactions remain relatively poorly understood, and most of our insight is gleaned by inference rather than actual mechanistic studies. For instance, the stereochemical outcome of thermal and photochemical extrusion of sulfur dioxide from 3‐sulfolenes provides complementary stereochemistry that is ascribed to the difference in the mechanism. The thermal extrusion is a disrotatory process according to the Woodward‐Hoffmann rules, whereas the corresponding photochemical process involves a conrotatory mechanism from an excited state intermediate. The mechanistic aspects of the extrusion of other groups, namely, sulfur monoxide, carbon monoxide, and molecular nitrogen illustrate the challenges in delineating a unified approach, given the subtle differences in each extrusion process. The section also describes how structural features in a series of bicyclic ketones provide insight for the observed extrusion rates, using kinetic studies and calculations.
The Scope and Limitations section is organized by the product (e.g., arenes, dihydroarenes, heterocycles, dienes, and polyenes) and then further subdivided by the type of extrusion (e.g., carbon monoxide, carbon dioxide, sulfur, sulfur dioxide, sulfur monoxide, selenium and tellurium, oxygen, and nitrogen), including reductive extrusion reactions. Notably, the extrusion process is subdivided by the nature of the dienophile often involved in the extrusion process, namely, benzynes, alkynes, alkenes, etc. A particular highlight is the extrusion of carbon monoxide from cyclopentadienone–polyacetylene adducts, which represents a powerful method for the iterative preparation of dendrimeric structures to form higher‐generation dendrimers. Additional sections focus on tandem extrusion reactions and include a section on ‘click’ reactions of triazines and tetrazines that showcase both creative and useful applications of this chemistry. The chapter also contains several sections on comparative studies, which, in conjunction with the Tabular Survey, provide the reader with the additional insight needed to select the appropriate precursor for the desired extrusion reaction.
The Applications to Synthesis section describes the use of the methodology to prepare arenes, heterocycles, dienes, and polyenes that have been subsequently employed to synthesize alkaloids and pheromones. There is also an extensive section on “click and release” reactions, which have been used in the development of prodrugs in medicinal chemistry. The Comparison with Other Methods section outlines a few related strategies for the de novo synthesis of arenes and 1,3‐dienes to provide the reader with a broader perspective on how the extrusion reactions compare with existing methods. The Tabular Survey incorporates reactions reported through early 2021. The organization mirrors the Scope and Limitations in that the reactions are organized by the product in the context of the type of extrusion process, which permits the identification of the optimal extrusion process for accessing a particular target. Overall, this is an excellent chapter on a venerable and important transformation relevant to modern synthetic, medicinal, and bioorganic chemistry.
I would be remiss if I did not acknowledge the entire Organic Reactions Editorial Board for their collective efforts in steering this volume through the editorial process' stages. I want to thank Dr. Stuart McCombie and Dr. Jin K. Cha, who served as Responsible Editors to marshal the chapter through the various phases of development. I am also deeply indebted to Dr. Danielle Soenen for her continued and heroic efforts as the Editorial Coordinator; her knowledge of Organic Reactions is critical to maintaining consistency in the series. Dr. Dena Lindsay (Secretary to the Editorial Board) is thanked for coordinating the authors', editors', and publishers' contributions. In addition, the Organic Reactions enterprise could not maintain the quality of production without the efforts of Dr. Steven M. Weinreb (Executive Editor), Dr. Engelbert Ciganek (Editorial Advisor), Dr. Landy Blasdel (Processing Editor), and Dr. Tina Grant (Processing Editor). I would also like to acknowledge Dr. Barry B. Snider (Secretary) for keeping everyone on task and Dr. Jeffery Press (Treasurer) for his fiscal diligence.
I am also indebted to past and present members of the Board of Editors and Board of Directors for ensuring the enduring quality of Organic Reactions. The specific format of the chapters, in conjunction with the collated tables of examples, makes this series of reviews both unique and exceptionally valuable to the practicing synthetic organic chemist.
P. Andrew Evans
Kingston
Ontario, Canada
CHAPTER 1EXTRUSION REACTIONS AFFORDING AROMATIC SYSTEMS, DIENES AND POLYENES
FRANK S. GUZIEC JR., LYNN JAMES GUZIEC, JIN K. CHA AND STUART MCCOMBIE
Department of Chemistry and Biochemistry, Southwestern University, Georgetown, TX, 78628
Edited by STUART MCCOMBIE AND JIN K. CHA
CONTENTS
ACKNOWLEDGMENTS
INTRODUCTION
MECHANISM AND STEREOCHEMISTRY
SCOPE AND LIMITATIONS
Arenes, Dihydroarenes and Other Aromatic Compounds via Extrusion Reactions
Arene and Dihydroarene Formation via Carbon Monoxide Extrusions
Arenes from Adducts of Cyclopentadienones
Dendrimer Formation from Adducts of Cyclopentadienones
Dihydroarenes via Reactions of Cyclopentadienones with Alkenes
Arenes and Dihydroarenes from Isolated Bicyclic Ketones
Other Aromatic Compounds from Cyclopentadienone Cycloadditions
Limitations on Cyclopentadienone‐Based Extrusion Reactions
Preparation of Cyclopentadienones and Bicyclic Adducts
Arenes by Double Extrusions of Carbon Monoxide from α‐Diketones
Extrusions of Carbon Dioxide
Arenes via Carbon Dioxide Extrusions from Cycloadducts of α‐Pyrones
Arenes and Dihydroarenes via Carbon Dioxide Extrusions from Cycloadducts of Mesoionic Compounds
Other Carbon Dioxide Extrusions
Arenes by Tandem Extrusions of Carbon Dioxide and Carbon Monoxide
Arenes and Aromatic Heterocycles via Extrusions of Sulfur
Aromatic Compounds via Extrusions of Sulfur from Heterocycles
Arenes and Aromatic Heterocycles from in Situ Generated Sulfur Intermediates
Arenes and Dihydroarenes via Extrusions of Sulfur Dioxide
Direct Extrusions of Sulfur Dioxide from Heterocycles
Arenes and Heterocycles via Extrusions of Sulfur Dioxide from δ‐Sultones, δ‐Sultams, and δ‐Thiosultones
Arenes and Heterocycles via Extrusions of Sulfur Dioxide from Benzosultones, Benzosultams and Benzothiosultones
Arenes and Dihydroarenes Derived from Adducts of Thiophene‐1,1‐dioxides
Preparation of Thiophene‐1,1‐dioxides
Arenes, Dihydroarenes and Aromatic Heterocycles via Extrusions of Sulfur Monoxide
Arenes and Aromatic Heterocycles by Direct Extrusions of Sulfur Monoxide from Heterocycles
Arenes and Dihydroarenes via Extrusions from Isolated Cycloadducts of Thiophene‐1‐oxides
Preparation of Thiophene‐1‐oxides
Reactivity of Thiophene‐1‐oxides
Arenes by Extrusions of Sulfur Species under Oxidative Conditions
Arenes and Aromatic Heterocycles via Extrusions of Selenium and Tellurium
Arenes, Dihydroarenes and Aromatic Heterocycles via Extrusions of Oxygen
‘Direct’ Extrusions of Oxygen
‘Indirect’ Extrusions of Oxygen
Other Extrusions of Oxygen
Preparation of Oxygenated Bicyclic Systems
Arenes and Heterocycles via Extrusions of Nitrogen Species
Molecular Nitrogen Extrusions via Cycloadditions
Solvent‐Directed Tetrazine Addition–Extrusions
‘Click’ Reactions of Triazines and Tetrazines
Pyrroles via Reduction–Nitrogen Extrusions
Other Molecular Nitrogen Extrusions
Arenes, Dihydroarenes and Other Aromatic Compounds via Extrusion Reactions: A Comparison
Dienes, Polyenes and Adducts via Extrusion Reactions
Medium‐Sized Ring Polyenes and Analogues via the Extrusions of Carbon Monoxide
Cyclic Polyenes by Extrusions of Carbon Dioxide
Dienes, Polyenes and Adducts via Extrusions of Sulfur Dioxide
Cyclic Polyenes by Extrusions of Sulfur Dioxide
Extrusions of Sulfur Dioxide from Sulfolenes
Dienes, Polyenes and Their Adducts by Extrusions of Sulfur Dioxide from 3‐Sulfolenes
Dienes, Polyenes and Their Adducts Derived from Ring‐Fused 3‐Sulfolenes
Preparation and Derivatization of 3‐Sulfolenes
Dienes and Polyenes from 2‐Sulfolenes
Dienes, Polyenes and Diones from Sulfolanes
Sulfur Dioxide Extrusions from Sultines
Diene Adducts via Sulfur Dioxide Extrusions from Sultines
Preparation of Sultines
Cyclooctatetraene Formation by Extrusion Reactions: a Comparison
APPLICATIONS TO SYNTHESIS
Arene and Heterocycle Syntheses
Diene, Polyene and Adduct Syntheses
‘Click and Release’ Reactions in Drug Discovery
COMPARISON WITH OTHER METHODS
De Novo Arene Syntheses
1,3‐Diene Synthesis
EXPERIMENTAL CONDITIONS
EXPERIMENTAL PROCEDURES
2,3,4,5‐Tetraphenylbenzoic Acid [Cycloaddition–Carbon Monoxide Extrusion of Tetracyclone]
1,2,3,4‐Tetraphenylnaphthalene [via Benzyne Cycloaddition–Carbon Monoxide Extrusion]
1,2,3,4‐Tetraphenylbiphenylene [Cycloaddition–Carbon Monoxide Extrusion]
Hexa‐[4‐(triisopropylsilylethynyl)phenyl]benzene [Dendrimer Core Formation via Cycloaddition–Carbon Monoxide Extrusion]
Tetracyclo[6.6.1.02,7.09,14]pentadeca‐3,5,10,12‐tetraene [Carbon Monoxide Extrusion from a Bicyclic Ketone]
Trimethyl 3,5‐Dimethyl‐1,2,4‐benzenetricarboxylate [Cycloaddition–Carbon Dioxide Extrusion of an α‐Pyrone]
Methyl 4‐Acetoxymethyl‐2,6‐dimethylbenzoate [Citric Acid‐Promoted Cycloaddition–Carbon Dioxide Extrusion of an α‐Pyrone]
4‐Ethyl‐bis[1,2]dithiolo[4,5‐
b
][5′,4′‐
d
]pyrrole‐3,5‐dione [via Thermal Extrusion of Sulfur from a Thiazine]
Diethyl 2,5‐Bis(trifluoromethyl)‐3,4‐pyrroledicarboxylate [Base‐Promoted Extrusion of Sulfur from a Thiazine]
Dimethyl 3‐Methoxy‐4‐methylphthalate [Cycloaddition–Extrusion of Sulfur from a Thiophene Adduct]
1,6,8,13‐Tetramethyl‐16‐phenyl‐7‐thiatetracyclo[13.3.0.0
2,12
.0
5,9
]octadeca‐1,5,8,12,14,18‐pentaene‐15,17‐dione [In Situ Oxidation–Extrusion of a Sulfoxide Bridge]
6,7,8,9‐Tetraphenylbenzocyclooctene [Zinc‐Promoted Reaction of 2,3,4,5‐Tetraphenylthiophene‐1,1‐dioxide with
trans
‐1,2‐Dibromo‐1,2‐dihydrobenzocyclobutene]
(2,3,4,5‐Tetrachloro‐6‐methylphenyl)acetic Acid [Cycloaddition–Sulfur Dioxide Extrusion of a 1,1‐Thiophene Dioxide]
Dimethyl 3,6‐Dimethylphthalate [Cycloaddition of an Alkyne to 2,5‐Dimethylfuran and Subsequent Ti(0)‐Promoted Extrusion of Oxygen]
6,6′‐[2‐Pyridyl]‐2,2′‐bipyridine [Conversion of a Bis‐triazine to a Bipyridine using Norborna‐2,5‐diene]
3‐Phenyl‐1‐(2‐pyridyl)‐5,6,7,8‐tetrahydroisoquinoline [Annulated Pyridine Formation via Nitrogen Extrusion from a Triazine]
(
E, Z
)‐5,7‐Dodecadiene [via Thermolysis of a
trans
‐Sulfolene]
(E, Z)
‐5,7‐Dodecadiene [via LAH Reduction of a
trans
‐Sulfolene]
(E, E)
‐5,7‐Dodecadiene [via Base‐Promoted Thermolysis of a
trans
‐Sulfolene]
2‐Ethoxycarbonyl‐3‐methoxy‐1,3‐butadiene [Sulfur Dioxide Extrusion via Flash Vacuum Pyrolysis of a 3‐Sulfolene]
4‐Carbomethoxy‐1,2,3,6‐tetrahydrophthalic Anhydride [Sulfur Dioxide Extrusion–Cycloaddition of a 3‐Sulfolene]
cis
‐
Dimethyl 2‐Benzyl‐5,6,7,8‐tetrahydro‐1‐oxo‐2
H
‐isoquinoline‐6,7‐dicarboxylate [Sealed‐Tube Sulfur Dioxide Extrusion–Cycloaddition of a 3‐Sulfolene]
