Phase-Transfer-Catalyzed Asymmetric Isomerization of Allylic Amines to Enamides via Kinetic Resolution.

An efficient kinetic resolution of allylic amines to enamides through phase-transfer-catalyzed asymmetric isomerization was developed. In the presence of a cinchona-derived ammonium salt and K3PO4·3H2O, a series of enamides containing a CF3-substituted chiral carbon and recovered allylic amines were obtained with excellent enantioselectivity and E/Z stereoselectivity. The utility of this method is showcased by a scale-up synthesis and transformations of the products.