The transition-metal-catalyzed isomerization of allylic alcohols or amines has been widely used to access -chiral carbonyl compounds and enamines (i.e., as in step 1 in Scheme 1b), respectively. Chirality is introduced by using metal complexes with specially designed chiral ligands. The synthesis of these ligands requires additional work, and the substrate scope of the reaction is dependent on the ligand used. An alternative method for the synthesis of carbonyl compounds with remote stereogenic centers is the stereospecific isomerization of -chiral allylic alcohols, which are easily accessible -chiral starting materials. These isomerization reactions can be mediated by achiral metal catalysts or by achiral bases, and take place through [1,3]-hydrogen shifts. The reaction takes place by a stepwise mechanism, so stereospecific examples are scarce. Our group has contributed to this field with the stereospecific isomerization of -trifluoromethylated allylic alcohols, ethers, and halides mediated by catalytic amounts of the base 1,5,7triazabicyclo[4.4.0]dec-5-ene (TBD; Figure ). Chirality is transferred from C to C in a stepwise manner, through the formation of a tight-ion-pair intermediate with induced noncovalent chirality (Figure ). When it comes to the basemediated isomerization of allylic amines yielding enamines, only one protocol has been reported to the best of our knowledge, which in this example is non-stereospecific. A related recent example is the base-mediated of -chiral allylic amides into axially chiral enamides. 25 In this work, we report a new method for the synthesis of chiral aliphatic amines with two stereogenic centers in noncontiguous positions. The method relies on a stereospecific TBD-mediated isomerization of -chiral allylic amines. As the reaction tolerates a further substituent at C, a subsequent reduction leads to functionalized aliphatic amines with two stereogenic centers, at C and at C, starting from readily available chiral allylic amines (Figure ). Importantly, the reaction works on primary allylic amines, so it represents a direct method for the synthesis of chiral primary amines. We started our investigations by designing an enantioselective synthesis of trifluoromethylated allylic amines (Scheme 1). Inspired by Guijarro's work on the synthesis of N-(tertbutylsulfinyl)imines, we subjected enone 1 to a titanium (IV) mediated, microwave-assisted reaction with (R)-2 to obtain the desired chiral sulfinimine (R)-3 in 70% yield. A diastereoselective reduction with DIBAL-H and a final acidic deprotection gave trifluoromethylated chiral allylic amine (R)-4a with 95% ee and in 42% yield over three steps.