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.