Rongalite addition to dienones: diastereoselectivity in cyclic sulfone synthesis; stereochemical rationalization and prospects as a general conjugate nucleophile

A detailed experimental and computational study of the diastereoselectivity of cyclic sulfone synthesis by reaction of Rongalite with doubly electrophilic dienones is presented. Computational methods, including density functional theory, conformational search methods, and internal reaction coordinate methods, have been used to rationalize the diastereoselectivity of the reaction by transition-state modeling, and showcases the conformational subtleties of sulfur-containing rings. Extension of the original reaction to double intermolecular additions is also demonstrated along with a comparative study of Rongalite with the reactivity of other readily available sulfinate nucleophiles using competition and exchange experiments.