Efficient Synthesis of Chiral Vicinal Diamines with Four Contiguous Stereocenters via Sequential Dynamic Kinetic Resolution of 2,3-Diamino-1,4-diones

The Ir/ f -PNNO complex catalyzed sequential dynamic kinetic resolution (DKR) of 2,3-diamino-1,4-diones has been successfully achieved, yielding acyclic vicinal diamines with four contiguous stereocenters in high yields and excellent diastereo- and enantioselectivity (> 20:1 dr and > 99% ee). This method exhibits a wide substrate scope and high efficiency, rendering it valuable for synthesizing functionalized chiral vicinal diamines. A gram-scale reaction performed with high efficiency at just 0.1 mol% catalyst loading, along with successful product derivatization, demonstrated the synthetic utility of this methodology. Mechanistic studies revealed that a stepwise DKR process was involved in this transformation.