Diastereomeric bisamidophosphites based on oxalamide 1,3-diol in asymmetric metal complex catalysis

Diastereomeric P*,P*-bisdiamidophosphite ligands of the 1,3,2-diazaphospholidine series bearing an oxalamide moiety have been synthesized. A possibility of their application in palladium- and rhodium-catalyzed asymmetric transformations was demonstrated. In Pd-catalyzed sulfonylation of (E)-1,3-diphenylallyl acetate with sodium p-toluenesulfinate enantioselectivity of up to 57% ee, in alkylation with dimethyl malonate of up to 77% ee, in amination with pyrrolidine of up to 78% ee, and in alkylation of cinnamyl acetate with ethyl 2-oxocyclohexane-1-carboxylate of up to 52% ee, in Rh-catalyzed hydrogenation of (Z-methyl 2-acetamido-3-phenylacrylate of up to 88% ee was achieved. An efficiency of diastereomeric chirality inducers was compared.