Copper-Catalyzed N-Directed Distal C(sp3)-H Sulfonylation and Thiolation with Sulfinate Salts.

We herein report a selective and catalytic C(sp3)-H functionalization approach to access amines bearing organo-sulfonyl and organo-thiol groups. This reaction proceeds through a cascade process of N-radical formation, alkyl radical formation via 1,5-HAT, and C-S bond formation, thereby offering a series of functionalized amines. This method could enable primary, secondary, and tertiary C(sp3)-H sulfonylation and thiolation and also exhibits good functional group tolerance.