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Full Description
In-depth monograph presenting innovative radical methodologies in the Brook rearrangement and their utility in organic synthesis
Radical Brook Rearrangement chronicles the evolution of radical Brook rearrangements, synthesizes recent advances in the field, and outlines future research directions. The book focuses on three key reactive intermediates — α-siloxy radicals, siloxycarbenes, and silenes — providing detailed analyses of their generation methods, substrate scope, mechanistic insights, and synthetic applications, along with practical experimental protocols.
Readers will find insights on alkoxy radical generation, photocatalytic systems, and the selection of radical/carbene acceptors. This book deliberately focuses on radical processes, excluding anionic pathways.
Written by a team of highly qualified researchers in the field, Radical Brook Rearrangement includes information on:
Generation of siloxycarbenes for metal siloxycarbene reaction, with information on aminooxycarbene reactions
Generation of siloxycarbenes for nucleophilic addition reaction, covering aldehydes and ketones as electrophiles and other electrophilic reagents
Generation of α-siloxy silyl radicals with (TMS)3SiOH, covering photoredox reactions and metallaphotoredox reactions with (TMS)3SiNHAd
Generation of α-siloxy radicals with α-silyl alcohol, covering metal-free, metal-catalyzed, photocatalyzed, and electrophotocatalyzed reactions
Containing cutting-edge research discoveries on the subject, Radical Brook Rearrangement is an essential reference for chemists across specializations, materials scientists, and professionals in the pharmaceutical industry.
Contents
Preface vii
Acknowledgments ix
List of Abbreviations xi
1 Introduction 1
References 5
2 Generation of α -Siloxy Radicals with α -Silyl Alcohols Through Radical Brook Rearrangement 7
2.1 Metal Free Reactions 7
2.2 Metal-catalyzed Reactions 8
2.3 Photocatalyzed Reactions 32
2.4 Electrophotocatalyzed Reactions 57
2.5 Other Reactions 59
References 66
3 Generation of α -Siloxy Radicals with Acylsilanes Through Radical Brook Rearrangement 69
3.1 Radical Initiation 69
3.2 Metal-catalyzed Reactions 76
3.3 Photocatalyzed Reactions 79
3.4 Other Reactions 84
References 85
4 Generation of α -Siloxy Silyl Radicals with (TMS)3SiOH Through Radical Brook Rearrangement 87
4.1 Metallaphotoredox Reactions 87
4.2 Photoredox Reactions 111
4.3 Metallaphotoredox Reactions with (TMS)3SiNHAd 125
References 142
5 Generation of Siloxycarbenes for Nucleophilic Addition Reaction 143
5.1 Aldehydes or Ketones as Electrophiles 143
5.2 Other Electrophilic Reagents 152
References 158
6 Generation of Siloxycarbenes for Insertion Reaction 161
6.1 Siloxycarbene Insertion Reactions into O--H Bond 161
6.2 Siloxycarbene Insertion Reactions into N--H Bond 167
6.3 Siloxycarbene Insertion Reactions into X--H Bond 172
6.4 Siloxycarbene Insertion Reactions into B--C Bond 184
6.5 Siloxycarbene Insertion Reactions into C--H Bond 197
References 211
7 Generation of Siloxycarbenes for Cycloaddition Reaction 213
7.1 [2 + 1] Cycloaddition with Alkynes 213
7.2 [2 + 1] Cycloaddition with Alkenes 222
7.3 [4 + 1] Cycloaddition Reaction with Dienes and α , β -Unsaturated Ketones 231
7.4 [2 + 2] Cycloaddition Reaction of α -Ketoacylsilanes with Imines 238
7.5 Other Reaction of Siloxycarbene 244
References 248
8 Metal Siloxycarbene and Aminooxycarbene Reaction 249
8.1 Metal Siloxycarbene Reactions 249
8.2 Aminooxycarbene Reactions 262
References 280
9 Generation of Silenes Through Radical Brook Rearrangement 283
9.1 Insertion Reactions 283
9.2 [2 + 2] Cycloaddition Reaction 290
9.3 [4 + 2] Cycloaddition Reaction 297
9.4 Other Reaction 303
References 309
Index 311
