β Elimination of a phosphonate group from an alkoxyl radical — Intramolecular acylation using acylphosphonate derivatives as carbonyl group acceptors

Abstract

The possibility of β elimination of a phosphonate group in radical reactions was studied. The facile β elimination of the phosphonate group from an alkoxyl radical was observed for the first time, whereas the β elimination of the phosphonate group from an aminyl and an alkyl radical did not occur. On the basis of our findings, the use of an acylphosphonate as a carbonyl group radical acceptor was investigated. Radical cyclization of the acylphosphonate in the presence of hexamethylditin in benzene at 300 nm for 2 h gave a cyclopentanone or a cyclohexanone derivative in good yield without the formation of a direct reduction product. The reaction can be carried out in the presence of a catalytic amount of hexamethylditin (0.2 equiv.) under similar conditions. In addition, an alkyl phosphonothiolformate group can act as an alkylthiocarbonyl group equivalent radical acceptor, providing ready access to a thiolactone synthesis.Key words: radical, β elimination, acylation, cyclization, acylphosphonate.