Regioselective Hydro(deutero)silylation of 1,3-Enynes Enabled by Photoredox/Nickel Dual Catalysis

In the presence of visible light irradiation, organophoto/nickel dual catalysts, and the mild base K₂HPO₄, 1,3-enynes react with silanecarboxylic acids to give the corresponding α-silylallenes with high selectivity. In this uniquely decarboxylative hydrosilylation of 1,3-enynes, a silyl radical process is involved and diverse electron-rich and -poor substrates proceed smoothly in moderate to excellent yields. This transformation is particularly synthetically worthwhile when using MeOD as the solvent, which furnishes new access to α-silyldeuteroallenes.