Influence on the enantioselectivity in allylic alkylation of the spacer between the amido group of d-glucosamine and the diphenylphosphino group

The synthesis of a new generation of chiral phosphine-amides derived from d-glucosamine is described. The palladium-catalyzed asymmetric allylic alkylation of racemic 1,3-diphenyl-2-propenyl acetate with dimethyl malonate has been investigated. The results obtained from these new ligands showed the importance of the rigidity of the complex and of the d-glucosamine skeleton on the enantioselectivity of the reaction.