Kinetic Resolution of Acyclic Tertiary Propargylic Alcohols by NHC-Catalyzed Enantioselective Acylation

Abstract

We report herein an efficient NHC-catalyzed kinetic resolution of acyclic tertiary propargylic alcohols that provides them in high to excellent enantioselectivity. This is the first example of kinetic resolution realized by enantioselective acylation. The recovered enantioenriched alcohols can be facilely converted into other valuable compounds such as densely functionalized tertiary alcohols and carbmates in high yields and excellent stereopurity. Density functional theory calculations were performed to determine the reaction mechanism and to understand the origin of enantiodiscrimination.

NHC-Catalyzed Reaction of Aldehydes for C(sp2)–O Bond Formation

“…Cascade redox esterification via NHC-linked homoenolate intermediates.4.3. Kinetic ResolutionThe kinetic resolution has been studied via chiral NHC-catalyzed oxidant-free redox esterification[155][156][157][158][159][160]. The kinetic resolution of racemic anilide rac-70 was achieved via redox esterification using alkynal 71 as a reducible substrate (Scheme 20)[155].…”