Nickel‐Catalyzed Enantioconvergent Carboxylation Enabled by a Chiral 2,2′‐Bipyridine Ligand

Abstract In contrast to previous approaches to chiral α‐aryl carboxylic acids that based on reactions using hazardous gases, pressurized setup and mostly noble metal catalysts, in this work, a nickel‐catalyzed general, efficient and highly enantioselective carboxylation reaction of racemic benzylic (pseudo)halides under mild conditions using atmospheric CO 2 has been developed. A unique chiral 2,2′‐bipyridine ligand named Me‐SBpy featuring compact polycyclic skeleton enabled both high reactivity and stereoselectivity. The utility of this method has been demonstrated by synthesis of various chiral α‐aryl carboxylic acids (30 examples, up to 95 % yield and 99 : 1 er), including profen family anti‐inflammatory drugs and transformations using the acids as key intermediates. Based on mechanistic experimental results, a plausible catalytic cycle involving Ni‐complex/radical equilibrium and Lewis acid‐assisted CO 2 activation has been proposed.

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