Iridium-Catalyzed, Asymmetric Amination of Allylic Alcohols Activated by Lewis Acids

Abstract

The direct, Ir-catalyzed, regio- and enantioselective amination of allylic alcohols with Lewis acid activators to form branched allylic amine products is reported. The reactions of arylamines, benzylic amines, and secondary aliphatic amines in the presence of Nb(OEt)5 as activator occurred with high regioselectivities and high enantioselectivities. These results led to the development of Ir-catalyzed reactions of allylic alcohol with arylamines and BPh3 as activator in catalytic amounts. These reactions are rare examples of enantioselective substitutions of allylic alcohols. They are particularly unusual examples of the substitution of allylic alcohols to generate branched substitution products from monosubstituted allylic alcohols and of enantioselective substitutions of allylic alcohols with amine nucleophiles.