In conclusion, an efficient method for the synthesis of novel chiral enamides scaffolds with a 𝛾-stereogenic trifluoromethyl-group has been established in high yields, outstanding enantiomeric excesses and excellent control of the E/Z geometry. Furthermore, this method tolerates a wide variety of electronic substituents and functional groups as demonstrated by the broad and diverse scope. This method is also applicable on a gram-scale and access to both enantiomers is possible. Additionally, a wide variety of new chiral, complex scaffolds were synthesized and a novel protocol for the E/Z isomerization of enamides has been established.