Pd-Catalyzed Stereodivergent Allylic Amination of α-Tertiary Allylic Alcohols towards α,β-Unsaturated γ-Amino Acids.

Abstract

Tertiary allylic alcohols were conveniently converted into either (Z)- or (E)-configured α,β-unsaturated γ-amino acids by treatment with secondary amines under Pd catalysis at ambient conditions. The key to control the stereochemical course of these formal allylic aminations was the presence of a suitable diphosphine ligand, with dppp [1,3-bis(diphenylphosphino)propane, L12] providing high yields and selectivities for the (Z) isomers, whereas the bis[(2-diphenylphosphino)phenyl]ether (DPEPhos) derivative L1' allowed for selective formation of the corresponding (E) isomeric products. This ligand-controlled, stereodivergent protocol thus shows promise for the stereoselective preparation of allylic amine products from a common substrate precursor.