Chemoselective α‐Alkylation of Nitriles with Primary Alcohols by Manganese(I)‐Catalysis

A sustainable and easy-to-use protocol for the alkylation of aryl nitriles with the earth-abundant manganese(I) catalyst is presented. The alkylation reaction employs readily available nitriles and naturally abundant alcohols as the coupling partners. The reaction proceeds chemoselectively and encompasses a broad substrate scope with good to excellent yields. The catalytic reaction yields selectively α-branched nitriles and water as the sole byproduct. Experimental studies were executed to understand the mechanism of the catalytic reaction.