Highly regio- and stereocontrolled preparation of α-(trifluoromethyl)-β-(phenylthio) enamines by the hydroamination of in situ -synthesized 1-(trifluoromethyl)-2-(phenylthio)ethyne.

Various nitrogen nucleophiles were easily added to in situ -generated 1-(trifluoromethyl)-2-(phenylthio)ethyne to afford the corresponding trifluoromethyl enamines in good-to-high yields and with high regio- and stereocontrol under very mild conditions.