Organocatalytic insertion into C–B bonds by in situ generated carbene: mechanism, role of the catalyst, and origin of stereoselectivity

Abstract

The origin of stereoselectivity for BINOL-catalyzed insertion into the C(sp2)-B bond of alkylboronic ester by in situ generated carbene has been investigated using density functional theory (DFT). The reaction to...

Asymmetric Organocatalytic Homologation: Access to Diverse Chiral Trifluoromethyl Organoboron Species

“…The proposed catalytic cycle (Scheme 5) is partially based on our previous assumptions [19] as well as on DFT modelling for Chemistry-A European Journal homologation of vinylboronates by Wang, Wei and coworkers. [22] The initial transesterification of BINOL 3 with 1 a leads to chiral boron intermediate A. Intermediate A is more reactive than 1 a.…”

Mechanistic insights into the Cu(ii)/DBU-catalyzed incorporation of CO2into homopropargylic amines

“…48 The mechanisms of the catalytic reactions were studied successfully by B3LYP. [49][50][51][52][53] As shown in Table S1 of the ESI, † CAM-B3LYP, BLYP, BHandHLYP, B3P86, and B3PW91 were employed to avoid the defects of functions. C, O, N, Cl, and H elements were described by the double-z basis set (6-31G*), [54][55][56] and the LanL2DZ basis set 57 was employed for the Cu element.…”

A DFT study on the mechanism and regioselectivity of NHC-catalyzed double acylation of aromatic 1,2-diketones with α,β-unsaturated ketones

“…We believe that this work can systematically solve the above questions based on our previous research experience. [33][34][35][36][37][38][39][40][41][42][43][44] Due to the reliability of density functional theory (DFT) 45 in the study of the mechanism of organocatalytic and transition metal catalytic reactions, M06-2X 46 in conjunction with the standard 6-31G(d,p) basis set was employed for all geometry optimizations. The solvent effect was considered using the implicit SMD model, and N,N-dimethylformamide 47 was the reaction solvent used in calculations.…”