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.