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

Tertiary allylic alcohols are conveniently converted into either (Z)‐ or (E)‐configured alfa,beta‐unsaturated gamma‐amino acids by treatment with secondary amines under Pd catalysis at ambient conditions. Key to control the stereoselective course of these formal allylic aminations is the presence of a suitable diphosphine ligand, with dppp [1,3‐diphenylphosphino)propane, L12] providing high yields and selectivities for the (Z) isomers, whereas the DPEPhos derivative L1´ allows for selective formation of the corresponding (E) isomeric products. This ligand‐controlled, stereodivergent protocol thus shows promise for the stereoselective preparation of allylic amination products from a common substrate precursor.