Moderately Oxidizing Thioxanthylium Organophotoredox Catalysts for Radical-Cation Diels-Alder Reactions.

Moderately oxidizing thioxanthylium photoredox catalysts that operate under irradiation with green light have been developed. These catalysts exhibit relatively moderate excited-state reduction potentials [ E 1/2 (C*/C •- ) = 1.75-1.94 V vs saturated calomel electrode (SCE)] and can efficiently promote radical-cation Diels-Alder reactions under irradiation with green light. Interestingly, β-halogenostyrenes ( E p/2 = 1.57-1.61 V vs SCE) are well tolerated, affording synthetically useful halocyclohexenes.