Radical Brook Rearrangement

Xiao Shen is Professor at the Institute for Advanced Studies, Engineering Research Center of Organosilicon Compounds & Materials, Ministry of Education, State Key Laboratory of Metabolism and Regulation in Complex Organisms, Wuhan University, China. He is the winner of 2025 RSC Fluorine Prize. He serves on the Advisory Board of Chem Catalysis, the Early-Career Advisory Board of Organic Chemistry Frontiers, and is an Early-Career Editorial Board Member for Chinese Chemical Letters and the Chinese Journal of Organic Chemistry.Yunxiao Zhang is a postdoctoral fellow of The Institute for Advanced Studies at Wuhan University, China.Gang Zhou is a postdoctoral fellow of The Institute for Advanced Studies at Wuhan University, China.

• Preface viiAcknowledgments ixList of Abbreviations xi1 Introduction 1References 52 Generation of α -Siloxy Radicals with α -Silyl Alcohols Through Radical Brook Rearrangement 72.1 Metal Free Reactions 72.2 Metal-catalyzed Reactions 82.3 Photocatalyzed Reactions 322.4 Electrophotocatalyzed Reactions 572.5 Other Reactions 59References 663 Generation of α -Siloxy Radicals with Acylsilanes Through Radical Brook Rearrangement 693.1 Radical Initiation 693.2 Metal-catalyzed Reactions 763.3 Photocatalyzed Reactions 793.4 Other Reactions 84References 854 Generation of α -Siloxy Silyl Radicals with (TMS)3SiOH Through Radical Brook Rearrangement 874.1 Metallaphotoredox Reactions 874.2 Photoredox Reactions 1114.3 Metallaphotoredox Reactions with (TMS)3SiNHAd 125References 1425 Generation of Siloxycarbenes for Nucleophilic Addition Reaction 1435.1 Aldehydes or Ketones as Electrophiles 1435.2 Other Electrophilic Reagents 152References 1586 Generation of Siloxycarbenes for Insertion Reaction 1616.1 Siloxycarbene Insertion Reactions into O─H Bond 1616.2 Siloxycarbene Insertion Reactions into N─H Bond 1676.3 Siloxycarbene Insertion Reactions into X─H Bond 1726.4 Siloxycarbene Insertion Reactions into B─C Bond 1846.5 Siloxycarbene Insertion Reactions into C─H Bond 197References 2117 Generation of Siloxycarbenes for Cycloaddition Reaction 2137.1 [2 + 1] Cycloaddition with Alkynes 2137.2 [2 + 1] Cycloaddition with Alkenes 2227.3 [4 + 1] Cycloaddition Reaction with Dienes and α , β -Unsaturated Ketones 2317.4 [2 + 2] Cycloaddition Reaction of α -Ketoacylsilanes with Imines 2387.5 Other Reaction of Siloxycarbene 244References 2488 Metal Siloxycarbene and Aminooxycarbene Reaction 2498.1 Metal Siloxycarbene Reactions 2498.2 Aminooxycarbene Reactions 262References 2809 Generation of Silenes Through Radical Brook Rearrangement 2839.1 Insertion Reactions 2839.2 [2 + 2] Cycloaddition Reaction 2909.3 [4 + 2] Cycloaddition Reaction 2979.4 Other Reaction 303References 309Index 311