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 AgBF 4 afforded a mixture of cationic palladium complexes: chelate [Pd(allyl) 1 ]BF 4 and head-to-head binuclear complex [Pd(allyl) 1 ] 2 (BF 4 ) 2 .