Bond cleavage

Catalysis

Polymer chemistry

Photochemistry

Radical disproportionation

Radical cyclization

Alkyl

Disproportionation

Medicinal chemistry

Organic chemistry

Reagent

Radical

Oxime

Chemistry

Synthesis

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

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