Mechanistic Aspects of Thiyl Radical-Promoted Acyl Radical Cyclization of Formylenoate-Cyclization versus Oxidation

Abstract

Treatment of formylalkenoates 1 and 7 with 2,2′-azobis(2-methylpropanenitrile) (AIBN) in the presence of dioxygen gave oxygenated carboxylic acids 5, 6, 8, 9 instead of acyl radical cyclization products, through preferential reaction of the corresponding acyl radicals with dioxygen rather than intramolecular attack to an enoate moiety. The reaction of 1 with AIBN in the absence of dioxygen recovered starting 1 in 98% yield.