LAUSR

A redox potential controlled intermolecular [2 + 2] cross-cycloaddition has been developed in the presence of a thioxanthylium photoredox catalyst. Electron-rich styrenes such as β-bromostyrene (Ep/2 = +1.61 V vs SCE) were selectively oxidized by a thioxanthylium photoredox catalyst (E1/2 (C*/C•-) = +1.76 V vs SCE) to styryl radical cations and reacted with styrene (Ep/2 = +1.97 V vs SCE) to furnish polysubstituted cyclobutanes in high yields. The present reaction can be successfully applied to intermolecular [2 + 2] cross-cycloaddition of β-halogenostyrenes, which cannot be effectively achieved by the hitherto reported representative organophotoredox catalysts.