Palladium catalyzed asymmetric reactions assisted by P*,P*-bidentate bisdiamidophosphites based on 1,4-diols

A small series of P*,P*-bidentate bisdiamidophosphite ligands containing 1,3,2-diazaphospholidine rings have been prepared. The cationic [Pd(allyl)(P*,P*)]BF4 and neutral [Pd(P*,P*)Cl2] palladium(II) complexes were synthesized with one of the new ligands. The use of these ligands provides up to 98% ee in Pd-catalyzed asymmetric allylations of (E)-1,3-diphenylallyl acetate, up to 72% ee in Pd-catalyzed asymmetric alkylation of cinnamyl acetate with ethyl 2-oxocyclohexane-1-carboxylate and up to 94% ee in Pd-catalyzed desymmetrization of N,N'-ditosyl-meso-cyclopent-4-ene-1,3-diol biscarbamate. The influence of the nature of the bridging ligand fragments of the bisdiamidophosphites on asymmetric induction is discussed.