P*,S-Bidentate diamidophosphite based on 3-(phenylthiomethyl)phenol

A new P*,S-bidentate diamidophosphite ligand 1, containing a stereogenic phosphorus atom as a part of the 1,3,2-diazaphospholidine ring, was synthesized based on 3-(phenylthiomethyl)phenol. Palladium catalysts on its basis demonstrated a high enantioselectivity in the allylic alkylation of (E)-1,3-diphenylallyl acetate with dimethyl malonate (76% ee), the amination with pyrrolidine (74% ee), and the alkylation of cinnamyl acetate with ethyl 2-oxocyclohexanecarboxylate (83% ee). The reaction of ligand 1 with [Pd(allyl)Cl]2 in the presence of AgBF4 afforded a mixture of cationic palladium complexes: chelate [Pd(allyl)1]BF4 and head-to-head binuclear complex [Pd(allyl)1]2(BF4)2.