Electroreductive Intramolecular Coupling of Aromatic Imino Esters: Is Four-Membered Cyclization Much More Favorable than Six-Membered Cyclization?

The electroreduction of an aromatic imino ester prepared from (S)-glutamic acid in the presence of chlorotrimethylsilane and triethylamine afforded a four-membered cyclized product, a mixed ketal of cis-2,4-disubstituted azetidine-3-one, stereospecifically. Calculations for the transition states by the DFT method support the predominant formation of the azetidine. The electroreduction of an aromatic imino ester prepared from (S)-aspartic acid gave almost equal amounts of a diastereomerically pure mixed ketal of cis-2,4-disubstituted azetidine-3-one and a diastereomeric mixture of 2,5-disubstituted pyrollidine-3-one.