Simultaneous Kinetic Resolution and Asymmetric Induction within a Borrowing Hydrogen Cascade Mediated by a Single Catalyst
Ming Yu Jin, Yali Zhou, Dengmengfei Xiao, Yipeng You, Qianqian Zhen, Guanyu Tao, Peiyuan Yu, Xiangyou Xing
Abstract
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.