First P*,S-bidentate diamidophosphite ligand in Pd-catalyzed asymmetric reactions

A novel P*,S-bidentate diamidophosphite ligand with a 1,3,2-diazaphospholidine core and an exocyclic thioether fragment provided up to 86% ee in the Pd-catalyzed alkylation of rac-(E)-1,3-diphenylallyl acetate with dimethyl malonate, as well as up to 73 and 75% ee in the amination of this substrate with pyrrolidine and diethyl (aminomethyl)phosphonate, respectively. For the Pd-catalyzed alkylation of cinnamyl acetate with β-keto esters, ee values up to 76% were achieved.