Cu-Catalyzed Tandem Oxidation-Intramolecular Cannizzaro Reaction of Biorenewables and Bioactive Molecules.

Abstract

A tandem Cu-catalyzed oxidation-intramolecular Cannizzaro reaction leading to bioactive α-hydroxyesters from α-hydroxyketones is reported. The process uses oxygen as a sole oxidant to achieve the formation of glyoxals, which are efficiently converted in situ to important α-hydroxyesters. The mechanistic insights are provided by isotopic labeling and supported by DFT calculations. The transformation proved a robust synthetic tool to achieve the synthesis of human metabolites and hydroxyl esters of various biologically active steroid derivatives.