Reversal in enantioselectivity for the palladium-catalyzed asymmetric allylic substitution with novel metallocene-based planar chiral diphosphine ligands

Abstract

The novel C 2-symmetric metallocene-based ligands with only planar chirality were synthesized easily and applied in palladium-catalyzed asymmetric allylic substitution with excellent enantioselectivity and high catalytic activity. When two ester groups on Cp rings of the metallocene were replaced by hydroxymethyl groups, opposite configuration of the product was obtained with high catalytic activity and excellent enantioselectivity. The opposite configuration of products was also obtained when the hydroxyl groups were protected as esters or ethers. These results might be attributed to the different configuration of the diphosphine ligands–Pd(II) complexes.