Relay C(sp³)-H bond trifluoromethylthiolation and amidation by visible light photoredox catalysis

Selective functionaliz0ation of C(sp³)–H bonds is a straightforward and practical method to construct complex molecule skeletons. In this field, direct transformation of unactivated C(sp³)–H bonds into C(sp³)–SCF₃ architectures is still a great challenge. We report a highly selective trifluoromethylthiolation of unactivated aliphatic C(sp³)–H bonds by combination of proton-coupled electron transfer (PCET) and hydrogen atom transfer (HAT) strategy. A wide range of structurally diverse alkyl trifluoromethyl sulfides are obtained. Furthermore, the use of two different photocatalysts can realize an unprecedented trifluoromethylthiolation and amidation cascade of different C(sp³)–H bonds. It can afford a good access to bifunctionalized molecules in synthetically useful yields.