The Mechanism of Iron(II)-Catalyzed Asymmetric Mukaiyama Aldol Reaction in Aqueous Media: Density Functional Theory and Artificial Force-Induced Reaction Study.

摘要: Density functional theory (DFT), combined with the artificial force-induced reaction (AFIR) method, is used to establish mechanism of aqueous Mukaiyama aldol reactions catalyzed by a chiral Fe(II) complex. On bases calculations, we identified several thermodynamically stable six- or seven-coordinate complexes in solution, where high-spin quintet state ground state. Among them, active intermediates for selectivity-determining outer-sphere carbon–carbon bond formation are proposed. The multicomponent (MC-AFIR) method found key transition states formation, and explained enantioselectivity diastereoselectivity. overall consists coordination aldehyde, rate-determining proton transfer from water dissociation trimethylsilyl group. calculated full catalytic cycle consistent experiments. This study provides i...