Y. Ogibin, A. Terent’ev, G. Nikishin
Jun 1, 1998
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Journal
Russian Chemical Bulletin
Abstract
A catalytic procedure has been developed for the synthesis of 15-pentadecanolide (1) from readily available 1-hydroperoxy-16-oxabicyclo[10.4.0]hexadecane (2). The method is based on the reaction of hydroperoxide2 with copper acetate (0.15–5 mol.%). Ring expansion occurred as a result of generation of tertiary bicyclohexadecyloxyl radicals4 from hydroperoxide2 under the action of Cu1 ions, β-scission of the radicals accompanied by regioselective cleavage of the bridge bond to form macrocyclic C-centered radicals5, and their oxidation by Cu11 ions to (E)-11- and (E)-12-pentadecen-15-olides (6). The products obtained were converted into 15-pentadecanolide by subsequent catalytic hydrogenation over a Pd catalyst in a yield of more than 90% with respect to hydroperoxide2.