ja511889y_si_001.pdf (15.29 MB)
A Phosphetane Catalyzes Deoxygenative Condensation of α‑Keto Esters and Carboxylic Acids via PIII/PVO Redox Cycling
journal contributionposted on 2015-01-21, 00:00 authored by Wei Zhao, Patrick K. Yan, Alexander T. Radosevich
A small-ring phosphacycle is found to catalyze the deoxygenative condensation of α-keto esters and carboxylic acids. The reaction provides a chemoselective catalytic synthesis of α-acyloxy ester products with good functional group compatibility. Based on both stoichiometric and catalytic mechanistic experiments, the reaction is proposed to proceed via catalytic PIII/PVO cycling. The importance of ring strain in the phosphacyclic catalyst is substantiated by an observed temperature-dependent product selectivity effect. The results point to an inherent distinction in design criteria for organophosphorus-based catalysts operating via PIII/PVO redox cycling as opposed to Lewis base (nucleophilic) catalysis.