A Bifunctional Copper Catalyst Enables Ester Reduction with H2: Expanding the Reactivity Space of Nucleophilic Copper Hydrides

Employing a bifunctional catalyst based on a copper(I)/NHC complex and a guanidine organocatalyst, catalytic ester reductions to alcohols with H₂ as terminal reducing agent are facilitated. The approach taken here enables the simul-taneous activation of esters through hydrogen bonding and formation of nucleophilic copper(I) hydrides from H₂, resulting in a catalytic hydride transfer to esters. The reduction step is further facilitated by a proton shuttle mediated by the guani-dinium subunit. This bifunctional approach to ester reductions for the first time shifts the reactivity of generally considered “soft” copper(I) hydrides to previously unreactive “hard” ester electrophiles and paves the way for a replacement of stoichi-ometric reducing agents by a catalyst and H₂.