There are numerous synthetic methods that allow the stereochemistry of  and chiral amines to be controlled. However, the synthesis of chiral amines with the stereogenic center at a remote position remains challenging. Buchwald and coworkers developed a copper(I)-catalyzed hydrocupration/alkoxide elimination reaction of allylic esters, followed by an anti-Markovnikov hydroamination of the olefin intermediate (Figure ). This method provides -chiral aliphatic amines with excellent enantioselectivities. However, it requires the use of specific electrophilic aminating reagents, and it is limited to tertiary amines. The Hull group contributed to this area with a Rh-catalyzed enantioselective isomerization/reductive amination of allylic diethyl amines (Figure ). In this case, the product of the redox-neutral isomerization process, a chiral enamine, reacts with amines in the presence of a reducing agent (NaBH4 or HCO2H), to give -chiral primary and secondary amine products with high enantioselectivities. To the best of our knowledge, these are the only two methods that have been reported for the synthesis of -chiral substituted aliphatic amines. Furthermore, neither of these methods tolerates further substitution at C and neither works with primary amines.