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A Phosphetane Catalyzes Deoxygenative Condensation of α‑Keto Esters and Carboxylic Acids via PIII/PVO Redox Cycling

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journal contribution
posted on 21.01.2015, 00:00 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/PVO 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/PVO redox cycling as opposed to Lewis base (nucleophilic) catalysis.