Radical Brook Rearrangement

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-siloxyl 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 minooxycarbene 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. 1. Introduction

2. Generation of a-siloxy radicals with a-silyl alcohols through radical Brook rearrangement
2.1 Radical initiated reactions
2.2 Metal-catalyzed reactions
2.3 Photocatalyzed reactions
2.4 Other reactions

3. Generation of a-siloxy radicals with acylsilanes through radical Brook rearrangement
3.1 Radical initiated reactions
3.2 Metal-catalyzed reactions
3.3 Photocatalyzed reactions

4. Generation of a-siloxy silyl radicals with (TMS)3SiOH through radical Brook rearrangement
4.1 Metallaphotoredox reactions
4.2 Photoredox reactions
4.3 Metallaphotoredox reactions with (TMS)3SiNHAd

5. Generation of siloxycarbenes for nucleophilic addition reaction
5.1 Aldehydes or ketones as electrophiles
5.2 Other electrophilic reagents

6. Generation of siloxycarbenes for insertion reactions
6.1 Carbene insertion reactions into O?H bonds
6.2 Carbene insertion reactions into N?H bonds
6.3 Carbene insertion reactions into other X?H bonds
6.4 Carbene insertion reactions into B?C bonds
6.5 Carbene insertion reactions into C?H bonds

7. Generation of siloxycarbenes for cycloaddition reactions
7.1 [2+1] cycloaddition with alkyne
7.2 [2+1] cycloaddition with alkene
7.3 [4+1] cycloaddition with diene
7.4 Other cyclization reactions

8. Generation of siloxycarbenes for metal siloxycarbene reactions

9. Generation of silenes through radical Brook rearrangement
9.1 Insertion reactions
9.2 Cycloaddition reactions
9.3 Other reactions

Xiao Shen is Professor at the Institute for Advanced Studies, Engineering Research Centre of

Organosilicon Compounds & Materials, Ministry of Education, Wuhan University, China. He is a member of the Youth Editorial Board of Chinese Chemical Letters.

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.