Strong and Confined Acids Control Five Stereogenic Centers in Catalytic Asymmetric Diels-Alder Reactions of Cyclohexadienones with Cyclopentadiene

Abstract

We describe a highly enantioselective Diels-Alder reaction of cross-conjugated cyclohexadienones with cyclopentadiene, in which five stereocenters are effectively controlled by a strongly acidic and confined imidodiphosphorimidate catalyst. Our approach provides tricyclic products in excellent stereoselectivity. We also report methods to convert the obtained products into useful intermediates and a computational study that aids in gaining deeper insight into the reaction mechanism and origin of stereoselectivity.

Keywords: Brønsted acids; Diels-Alder reaction; cyclohexadienones; imidodiphosphorimidates; organocatalysis.