Copper-Catalyzed Remote C(sp³)–H Phosphorothiolation of Sulfonamides and Carboxamides in a Multicomponent Reaction

The catalytic C(sp³)-H functionalization is highly desirable yet challenging in organic synthesis. Incorporation of the SP(O)(OR)₂ group through C(sp³)-H functionalization remains unexplored. We herein report an unprecedented protocol for phosphorothiolation of primary and secondary C(sp³)-H via a multicomponent reaction with N-fluoro-substituted amides, elemental sulfur, and P(O)H compounds involving a sequence of amidyl radical generation, 1,5-HAT, and a Cu-catalyzed cross coupling of the resulting carbon radical with (RO)₂P(O)SH (generated in situ).