Mechanistic insight into B(C₆F₅)₃ catalyzed imine reduction with PhSiH₃ under stoichiometric water conditions.

ABSTRACT: A DFT and experimental study on the mechanism of B(C₆F₅)₃ catalyzed imine reduction is performed using PhSiH₃ as reductant under stoichiometric water conditions. Ingleson's path B is reconfirmed here. And four novel (C₆F₅)₃B-OH₂ induced pathways (paths C2, C3, D2 and D3) entirely different from all the previous mechanisms were determined for the first time. They are all B(C₆F₅)₃ and water/amine catalyzed cycles, in which the nucleophilic water or amine catalyzed addition step between PhSiH₃ and the N-silicon amine cation is the rate-determining step of paths C2/D2 and C3/D3 with activation Gibbs free energy barriers of 23.9 and 18.3 kcal mol^-1

SUBMITTER: He Y 

PROVIDER: S-EPMC9034009 | biostudies-literature | 2021 Jun

REPOSITORIES: biostudies-literature