Generation of β-Carbonyl Radicals from Cyclopropanol Derivatives by the Oxidation with Manganese(III) 2-Pyridinecarboxylate and Their Reactions with Electron-Rich and -Deficient Olefins

Abstract

Abstract Various β-carbonyl radicals are generated oxidatively from cyclopropanol derivatives by the use of manganese(III) 2-pyridinecarboxylate (Mn(pic)3). These β-carbonyl radicals react with electron-rich olefins such as conjugated silyl enol ethers, a ketene thioacetal, a ketene dithioacetal, and a vinyl ether intermolecularly to give crossed-addition products in good yield. Furthermore, the combined use of Mn(pic)3 and tributylhydridotin makes it possible to carry out the 1 : 1 addition reaction of these β-carbonyl radicals with electron-deficient olefins such as acrylonitrile, acrylaldehyde, methyl acrylate, methyl vinyl ketone, and N,N-dimethylacrylamide, and the corresponding products are obtained in moderate to good yield.