A New Family of Nucleophiles for Photoinduced, Copper-Catalyzed Cross-Couplings via Single-Electron Transfer: Reactions of Thiols with Aryl Halides Under Mild Conditions (0 °C)

Abstract

Building on the known photophysical properties of well-defined copper–carbazolide complexes, we have recently described photoinduced, copper-catalyzed N-arylations and N-alkylations of carbazoles. Until now, there have been no examples of the use of other families of heteroatom nucleophiles in such photoinduced processes. Herein, we report a versatile photoinduced, copper-catalyzed method for coupling aryl thiols with aryl halides, wherein a single set of reaction conditions, using inexpensive CuI as a precatalyst without the need for an added ligand, is effective for a wide range of coupling partners. As far as we are aware, copper-catalyzed C–S cross-couplings at 0 °C have not previously been achieved, which renders our observation of efficient reaction of an unactivated aryl iodide at −40 °C especially striking. Mechanistic investigations are consistent with these photoinduced C–S cross-couplings following a SET/radical pathway for C–X bond cleavage (via a Cu(I)–thiolate), which contrasts with nonphotoinduced, copper-catalyzed processes wherein a concerted mechanism is believed to occur.

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