Asymmetric Allylic Amination of Morita-Baylis-Hillman Adducts with Simple Aromatic Amines by Nucleophilic Amine Catalysis

Asymmetric allylic amination of Morita-Baylis-Hillman (MBH) adducts with simple aromatic amines is successfully realized by nucleophilic amine catalysis. A range of substituted -methylene--arylamino esters is accessed in moderate to high yields (up to 88%) and with excellent enantioselectivities (up to 97% ee). Inorganic fluorides are found to be able to improve the enantioselectivity of the allylic amination reaction. A pyrrole-2-carboxylate and a cyclic imide are also compatible with this catalytic system. A chiral 2,3-dihydroquinolin-4-one derivative is easily obtained from the allylic amination product.