Ambient-Temperature Newman–Kwart Rearrangement Mediated by Organic Photoredox Catalysis

The Newman–Kwart rearrangement is perhaps the quintessential method for the synthesis of thiophenols from the corresponding phenol. However, the high thermal conditions required for the rearrangement of the requisite O-aryl carbamo­thioates often leads to decomposition. Herein, we present a general strategy for catalysis of O-aryl carbamo­thioates to S-aryl carbamo­thioates using catalytic quantities of a commercially available organic single-electron photo­oxidant. Importantly, this reaction is facilitated at ambient temperatures.