Efficient synthesis of chiral vicinal diamines with four contiguous stereocenters via sequential dynamic kinetic resolution of 2,3-diamino-1,4-diketones.

Abstract

The stereoselective construction of chiral vicinal diamines bearing multiple contiguous stereocenters remains a formidable challenge in modern organic synthesis. Herein, we report an Ir-catalyzed sequential dynamic kinetic resolution of 2,3-diamino-1,4-diketones that furnishes acyclic vicinal diamines containing four contiguous stereocenters in high yields with excellent diastereo- and enantioselectivity. The protocol exhibits broad substrate generality and high catalytic efficiency, enabling streamlined access to structurally diverse, functionally enriched chiral vicinal diamines. A gram-scale reaction proceeds smoothly with only 0.1 mol% catalyst loading, and versatile downstream derivatizations further highlights the synthetic utility of the method. Mechanistic investigations support a stepwise dynamic kinetic resolution pathway operative in this transformation.