Chiral Molecular Tweezers: Synthesis and Reactivity in Asymmetric Hydrogenation

We report the synthesis and reactivity of a chiral aminoborane displaying both rapid and reversible H-2 activation. The catalyst shows exceptional reactivity in asymmetric hydrogenation of enamines and unhindered imines with stereoselectivities of up to 99% ee. DFT analysis of the reaction mechanism pointed to the importance of both repulsive steric and stabilizing intermolecular non-covalent forces in the stereodetermining hydride transfer step of the catalytic cycle.