Enantioselective Synthesis of 1,2-Diamines Containing Tertiary and Quaternary Centers through Rhodium-Catalyzed DYKAT of Racemic Allylic Trichloroacetimidates

The amination of racemic secondary
and tertiary allylic trichloroacetimidates
possessing β-nitrogen substituents and proximal nitrogen-containing
heterocycles, via chiral diene-ligated rhodium-catalyzed dynamic kinetic
asymmetric transformations (DYKAT), provides branched allylic 1,2-diamines
with high enantioselectivity. The catalytic system can be applied
to the synthesis of 1,2-diamines possessing two contiguous stereocenters
with excellent diastereoselectivity. Furthermore, the nitrogen-containing
heterocycles suppress competing vinyl azirdine formation, allowing
for the high enantioselective syntheses of 1,2-diamines possessing
tertiary and quaternary centers.