Journal of the American Chemical Society, Vol.139, No.24, 8126-8129, 2017
Enantioselective CuH-Catalyzed Hydroacylation Employing Unsaturated Carboxylic Acids as Aldehyde Surrogates
The direct asymmetric copper hydride (CuH)-catalyzed coupling of alpha,beta-unsaturated carboxylic acids to aryl alkenes to access chiral alpha-aryl dialkyl ketones is reported. A variety of substrate substitution patterns, sensitive functional groups, and heterocycles are tolerated in this reaction, which significantly expands the range of accessible products compared with existing hydroacylation methodology. Although mechanistic studies are ongoing, we propose that CuH-catalyzed silylation of unsaturated acids occurs to access a uniquely effective acyl electrophilic coupling partner.