Photocatalytic 1,2-Thiosulfonylation of Alkenes with Thiophenols and Sulfonyl Chlorides Promoted by Directly Knitted Copper Polymers

Considering the importance of organosulfur compounds in synthetic and biological chemistry, copper-containing hypercrosslinked polymers (HCPs-Cu 1a-d) with uniformly dispersed Cu centers were prepared by using the “direct knitting” strategy without any premodification, which exhibited outstanding catalytic activity towards visible light-promoted three-component 1,2-thiosulfonylation of alkenes with thiophenols and sulfonyl chlorides. Besides the remarkably broad substrate scopes featuring diverse electronic properties, functional groups and heterocycles (56 examples), and good activity (up to 96%), solid HCP-Cu 1a could be reused up to 8 times without loss of catalytic activity. Notably, the ease of scaling up to gram-scale and late-stage functionalizations of a myriad of alkene-containing natural products and drug molecules (15 examples) highlighted the great synthetic utility of HCP-Cu 1a as a competitive photocatalyst.