posted on 2015-01-21, 00:00authored byWei 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.