An efficient intermolecular atom-transfer addition reaction of alkynes via the combination of visible-light photoredox catalysis and gold catalysis has been developed, affording diverse trifluoromethylthio- and difluoromethylthio-functionalized vinylsulfones with high stereoselectivity in good yields. Thiosulfonylation reaction of enyne can also be realized for constructing functionalized carbo- and heterocycles through a radical cascade cyclization process. These reactions proceed through a gold-assisted sulfonyl radical addition pathway.

Polysulfide anions are endowed with unique redox properties, attracting considerable attentions for their applications in alkali metals−sulfur batteries. However, the employment of these anionic species in redox catalysis for small molecule synthesis remains underdeveloped due to their moderate−poor electrochemical potential in the ground state, whereas some of them are characterized by photoabsorptions in visible spectral regions. Herein, we disclose the use of polysulfide anions as visible light photoredox catalysts for aryl cross-coupling reactions. The reaction design enables single-electron reduction of aryl halides upon the photoexcitation of tetrasulfide dianions (S 4 2− ). The resulting aryl radicals are engaged in (hetero)biaryl cross-coupling, borylation, and hydrogenation in a redox catalytic regime involving S 4• − /S 4 2− and S 3 • − /S 3 2− redox couples.

An unprecedented intermolecular atom transfer thiosulfonylation reaction of alkenes was achieved by combining Au catalysis and visible-light photoredox catalysis. A SCF3 group and other functionalized thio groups together with sulfonyl group were regioselectively introduced into alkenes.

A scandium(iii)-catalyzed electrophilic alkene difunctionalization reaction with the synergistic formation of two C–S bonds has been developed. This reaction features a broad substrate scope, simple procedures, 100% atom economy, and a reversed regioselectivity compared to previously studied alkene sulfonylation methods.