Computational Insight into the Enantioselective Nucleophilic Borylation of a Polarized CO Double Bond Catalyzed by Diphosphine/Borylcopper(I) Complexes

Density functional theory calculations were performed to validate the proposed reaction mechanism for the enantioselective nucleophilic borylation of a polarized CO double bond in the presence of diphosphine/borylcopper­(I) complexes. Consequently, we successfully elucidated the origin for the regioselectivity and the mechanism for the enantioselectivity of the reaction. We also obtained theoretical explanations for the fact that the presence of a proton source gave a higher reactivity and a better enantioselectivity in the borylation reaction of aldehydes with a copper­(I)/(R)-DTBM-SEGPHOS complex catalyst. This study is particularly valuable toward the development and design of novel enantioselective borylation reactions with polarized carbon–heteroatom double bonds.