Having developed this enantioselective protocol for the synthesis of chiral trifluoromethylated allylic amines, we went on to examine the base-catalyzed stereospecific isomerization of -trifluoromethylated allylic amine 4a. When allylic amine 4a is treated with base, it undergoes isomerization to give a mixture of the primary enamine and the imine, as observed by NMR spectroscopy, which cannot be isolated. We therefore hydrolyzed this mixture by treatment with HCl (2 M) to give the corresponding chiral ketone, from which we could determine the efficiency of the chirality transfer. We found that when 4a was treated with catalytic amounts of TBD, it underwent the isomerization reaction to yield ketone 5a in quantitative yield and with high levels of chirality transfer (c.t.; Table , entry 1). The reaction also took place in the presence of a catalytic amount of 1,8-diazabicyclo[5.4.0]undec-7-ene (DBU) or MTBD (N-methyl TBD), although the yields were significantly lower (Table , entries 2 and 3 vs entry 1). Catalytic amounts of the more basic phosphazene P4-t-Bu did not yield 5a. This result indicates that the reaction relies not only on the basicity of the catalyst, but also on the ability of its conjugate acid to protonate the allylic anion intermediate (Table , entry 4). Decreasing the temperature to 60 ˚C did not show any significant effect on either the conversion or the chirality transfer (Table , entry 5), and the reaction did not work at room temperature (Table , entry 6). As expected, solvents that can be deprotonated did not give the product (Table and). In polar aprotic solvents such as 1,4-dioxane and ethyl acetate, the yields were similar to those obtained in toluene, but the chirality transfer was less efficient (Table , entries 9 and 10 vs entry 5). Finally, the effect of the catalyst loading was studied, and 5% of TBD was found to be sufficient for the reaction to take place in high yield, and, importantly, with an increased chirality transfer of 95% (Table , entry 11). Any further decrease in the catalyst loading was found to be detrimental to the reaction (Table , entry 12).