P,S-Bidentate Phosphoramidites with (Ra)-BINOL Core in Palladium-Catalyzed Asymmetric Allylic Substitution

Abstract

New P,S-bidentate phosphoramidite ligands, including these having a stereogenic phosphorus atom in the 1,3,2-dioxaphosphepine ring, have been synthesized on the basis of (Ra)-BINOL and its adamantanyl derivatives. With their participation in the Pd-catalyzed asymmetric allylic alkylation of (E)-1,3-diphenylallyl acetate with dimethyl malonate and the amination with pyrrolidine involving these ligands have afforded selectivity up to 84 and 75% ee, respectively.