Iridium-Catalyzed Allylic Amination of Allylic Alcohols

One stoichiometric and one catalytic iridium-catalyzed allylic amination of terminal allylic alcohols forming branched allylic amines in high regio- and enantioselectivity are reported. The activator for the stoichiometric process is Nb(OEt)5 with substoichiometric amounts leading to lower reaction rates and selectivities. The catalytic process favors the use of triphenylboron. Both processes use a chiral phosphoramidite ligand for enantioselective induction. The scope for both methods includes a variety of arylamines and aryl and aliphatic allylic alcohols, producing almost exclusively branched products with high ee values.