Palladium and rhodium-catalyzed enantioselective reactions mediated by pseudodipeptide-based phosphite-type ligand

Abstract

P*-Chiral diamidophosphite ligand of a 1,3,2-diazaphopholidine series bearing the exocyclic pseudodipeptide fragment was synthesized. The possibility of its application in the palladium- and rhodium-catalyzed asymmetric transformations was demonstrated. This ligand provided up to 84% ee in the Pd-catalyzed alkylation of (E)-1,3-diphenylallyl acetate with dimethyl malonate, up to 56% ee in amination of this substrate with pyrrolidine, and up to 68% ee in alkylation of cinnamyl acetate with ethyl 2-oxocyclohexane-1-carboxylate. In the Rh-catalyzed hydrogenation of (Z)-methyl 2-acetamido-3-phenylacrylate mediated by this ligand, up to 53% ee was achieved.