Intermolecular Photocatalytic Chemo‐, Stereo‐ and Regioselective Thiol–Yne–Ene Coupling Reaction

The first example of an intermolecular thiol–yne–ene coupling reaction is reported for the one‐pot construction of C−S and C−C bonds. Thiol–yne–ene coupling opens a new dimension in building molecular complexity to access densely functionalized products. The employment of Eosin Y/DBU/MeOH photocatalytic system suppresses hydrogen atom transfer (HAT) and associative reductant upconversion (via C−S three‐electron σ‐bond formation). Investigation of the reaction mechanism by combining online ESI‐UHRMS, EPR spectroscopy, isotope labeling, determination of quantum yield, cyclic voltammetry, Stern–Volmer measurements and computational modeling revealed a unique photoredox cycle with four radical‐involving stages. As a result, previously unavailable products of the thiol–yne–ene reaction were obtained in good yields with high selectivity. They can serve as stable precursors for synthesizing synthetically demanding activated 1,3‐dienes.