A General Mechanistic Scheme for Intramolecular Electrochemical Hydrocyclizations. Mechanism of the Electroreductive Cyclization of ω-Keto-α,β-unsaturated Esters

Article abstract of DOI:10.1021/jo00096a054

A systematic procedure is suggested for formulating possible mechanisms by which electrochemical hydrocyclization and dehydrocyclization can occur.A combination of linear sweep voltammetry (LSV) and chemical and electrochemical arguments can be used to reduce the mechanistic possibilities to a small set or even a unique mechanism.The procedure is applied to the reductive cyclization of ω-keto-α,β-unsaturated esters.Of the several hundred mechanistic possibilities for this process, the combination of LSV and chemical arguments can reduce the list to four; preparative-scale electrolysis of a specially designed substrate permits assignment of a unique mechanism, the e-P-d-c-p path, at low concentrations of electroactive substance.