Mechanistic insights into excited-state palladium catalysis for C-S bond formations and dehydrogenative sulfonylation of amines.

Photocatalytic selective C(sp 3 )-H activation/cross-coupling reactions are appealing in organic synthesis. In this manuscript, we describe the development of photoexcited-state Pd-catalyzed dehydrogenative β-sulfonylation reactions using amines and aryl sulfonyl chlorides via intermolecular hydrogen atom transfer and C-S cross-coupling processes at room temperature. The transformation can be achieved by the direct generation of two distinct Pd-radical hybrid species and their capability to promote two different reactivities from Pd(0) and aryl sulfonyl chlorides, allowing for the efficient conversion of readily available amines into stable sulfonyl-substituted enamines at room temperature. The in-depth experimental, computational, and transient optical spectroscopic study and catalytic applications of a dehydrogenative functionalization event provide evidence for both static and dynamic quenching, as well as inner-sphere and outer-sphere mechanisms.