Mechanistic insights into rhodium-catalyzed enantioselective allylic alkylation for quaternary stereogenic centers.

ABSTRACT: Installing quaternary stereogenic carbon is an arduous task of contemporary importance in the domain of asymmetric catalysis. To this end, an asymmetric allylic alkylation of α,α-disubstituted aldehydes by using allyl benzoate in the presence of Wilkinson's catalyst [Rh(Cl)(PPh₃)₃], (R)-BINOL-P(OMe) as the external ligand, and LiHMDS as the base has been reported to offer high enantioselectivity. The mechanistic details of this important reaction remain vague, which prompted us to undertake a detailed density functional theory (SMD_(THF)/B3LYP-D3) investigation on the nature of the potential active catalyst, energetic features of the catalytic cycle, and the origin of high enantioselectivity. We note that a chloride displacement from the native Rh-pho

SUBMITTER: Pareek M 

PROVIDER: S-EPMC8179253 | biostudies-literature | 2020 Dec

REPOSITORIES: biostudies-literature