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