Iminyl-Radical-Triggered C–C Bond Cleavage of Cycloketone Oxime Derivatives: Generation of Distal Cyano-Substituted Alkyl Radicals and Their Functionalization

Alkyl nitriles are versatile building blocks in organic synthesis because the cyano group can be easily converted into other functional groups. Iminyl-radical-triggered C–C bond cleavage of cycloketone oxime­ derivatives provides a practical route to access distal cyano-substituted alkyl radicals, which has given chemists a new radical reaction platform for the synthesis of diverse alkyl nitriles. This review provides an overview of various types of radical cyanoalkylation via ring opening of cycloketone oxime derivatives.

1 Introduction

2 C–C Bond Formation

2.1 Alkenes as Radical Acceptors

2.2 Aromatic Rings as Radical Acceptors

2.3 Organometallic Reagents as Radical Acceptors

2.4 Cyanoalkyl-Radical-Triggered Cyclization Reactions

2.5 Miscellaneous

3 C–Heteroatom Bond Formation

3.1 C–O Bond Formation

3.2 C–N Bond Formation

3.3 C–S Bond Formation

3.4 C–Halogen Bond Formation

3.5 C–B Bond Formation

4 Conclusion