γ-CF 3 -Allenamides versus 3-CF 3 -Cyclopentenylamines: Substituent-Controlled Divergent Reaction of β-CF 3 -1,3-Enynamides with β-Dicarbonyl Compounds.

A distinctive N -substituent-controlled regioselective 1,4-hydrocarbonation or 1,4-hydrocarbonation/5- endo - trig cyclization cascade reaction of β-CF 3 -1,3-enynamides with β-dicarbonyl compounds in the presence of a simple base is reported. β-CF 3 -1,3-enynamides having a Ts group N -substituent produce γ-CF 3 -allenamides via a 1,4-hydrocarbonation process, whereas β-CF 3 -1,3-enynamides bearing a Ms group N -substituent lead to 3-CF 3 -cyclopentenylamines through a 1,4-hydrocarbonation/5- endo - trig cyclization cascade process.