Single-Carbon Insertion into Single C–C Bonds with Diazirines

A novel platform for the skeletal editing of single C–C bonds via a single-carbon insertion has been developed using diazirines. This strategy involves the photogeneration of arylchlorocarbenes as carbynoid species that undergo site-selective carbene insertion into tertiary C–H bonds and a subsequent Wagner–Meerwein rearrangement promoted by a silver salt. Our skeletal editing strategy based on a formal selective carbyne C–C bond insertion has been demonstrated in six core-to-core conversions, including linear and cyclic benzylic substrates, alkanes and late-stage functionalizations.