Simultaneous Kinetic Resolution and Asymmetric Induction within a Borrowing Hydrogen Cascade Mediated by a Single Catalyst

The mechanistic uniqueness and versatility of borrowing hydrogen catalysis provides an opportunity to investigate the controllability of a cascade reaction, and more importantly, to realize either one or both of chiral recognition and chiral induction simultaneously. Here we report that, in a borrowing hydrogen cascade starting from racemic allylic alcohols, one of the enantiomers could be kinetically resolved, while the other enantiomer could be purposely converted to various targeted products, including α,β‐unsaturated ketones, β‐functionalized ketones and γ‐functionalized alcohols. By employing a robust Ru‐catalyst, both kinetic resolution and asymmetric induction were achieved with remarkable levels of efficiency and enantioselectivity. Density functional theory (DFT) calculations suggest that corresponding catalyst–substrate π–π interactions are pivotal to realize the observed stereochemical diversity. Highly chemo‐ and stereoselective borrowing hydrogen processes are reported in which various target products are obtained through fine‐tuning of the reaction conditions. By employing a robust Ru‐catalyst of minimal stereogenicity, both kinetic resolution and asymmetric induction were achieved simultaneously through a borrowing hydrogen cascade.