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Cu-Catalyzed Tandem Oxidation-Intramolecular Cannizzaro Reaction of Biorenewables and Bioactive Molecules
Hristo Petkov1, Martin A Ravutsov1, Manuel J Verganista2
1Institute of Organic Chemistry with Centre of Phytochemistry Bulgarian Academy of Sciences, Acad. G. Bonchev str., bl. 9, Sofia, 1113, Bulgaria.
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.
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