Preface vii

Acknowledgments ix

List of Abbreviations xi

1 Introduction 1

References 5

2 Generation of ¿ -Siloxy Radicals with ¿ -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 ¿ -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 ¿ -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 ¿ , ß -Unsaturated Ketones 231

7.4 [2 + 2] Cycloaddition Reaction of ¿ -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