A General Approach to Site‐Specific, Intramolecular C−H Functionalization Using Dithiocarbamates

Intramolecular hydrogen atom transfer is an established approach for the site‐specific functionalization of unactivated, aliphatic C−H bonds. Transformations using this strategy typically require unstable intermediates formed using strong oxidants and have mainly targeted C−H halogenations or intramolecular aminations. Herein, we report a site‐specific C−H functionalization that significantly increases the synthetic scope and convergency of reactions proceeding via intramolecular hydrogen atom transfer. Stable, isolable N ‐dithiocarbamates are used as precursors to amidyl radicals formed via either light or radical initiation to efficiently deliver highly versatile alkyl dithiocarbamates across a wide range of complex structures.