Photoredox catalyzed C-C bond formation at unactivated sp3 C-H bonds. a, Trifluoroacetamide as the directing group for C-H functionalization. b, Scope of C-C bond formation with respect to the alkene. c, Scope of C-C bond formation with respect to the amine. Solvent is benzotrifluoride unless otherwise indicated. Bn: benzyl; Bu: butyl; dr: diastereomeric ratio; Et: ethyl; Me: methyl; rac: racemic; tBu: tert-butyl; TBS: tert-butyldimethylsilyl; Boc: tert-butyloxycarbonyl; Ph: phenyl; DMF: dimethylformamide; tAmOH: tert-amyl alcohol; dF-CF3ppy: 2-(2,4-difluorophenyl)-5-trifluoromethylpyridine; dtbbpy: 4,4′-di-tert-butyl-2,2′-bipyridine.