α-Phenylthioaldehydes for the effective generation of acyl azolium and azolium enolate intermediates.

ABSTRACT: α-Phenylthioaldehydes are readily prepared using a simple multi-step procedure and herein are introduced as a new precursor for the NHC-catalysed generation of acyl azolium and azolium enolate intermediates that are of widespread synthetic interest and utility. Treatment of α-phenylthioaldehydes with an NHC precatalyst and base produces an efficient redox rearrangement via a Breslow intermediate, elimination of thiophenolate, and subsequent rebound addition to the generated acyl azolium to give the corresponding thiol ester. In the presence of an external alcohol, competition between redox rearrangement and redox esterification can be controlled through judicious choice of the N-aryl substituent within the NHC precatalyst and the base used in the reaction. With NEt₃

SUBMITTER: Ewing PMDA 

PROVIDER: S-EPMC11186317 | biostudies-literature | 2024 Jun

REPOSITORIES: biostudies-literature