Rhodium-Catalyzed Dynamic Kinetic Asymmetric Transformations of Racemic Tertiary Allylic Trichloroacetimidates with Anilines

The rhodium-catalyzed regio- and enantioselective amination
of
racemic tertiary allylic trichloroacetimidates with a variety of aniline
nucleophiles is a direct and efficient route to chiral α,α-disubstituted
allylic N-arylamines. We describe the first dynamic
kinetic asymmetric transformations of racemic tertiary allylic electrophiles
with anilines utilizing a chiral diene-ligated rhodium catalyst. The
method allows for the formation of α,α-disubstituted allylic N-arylamines in moderate to good yields with good to excellent
levels of regio- and enantioselectivity.