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.