Shanghai Key Laboratory for Molecular Engineering of Chiral Drugs, Frontier Science Center for Transformative Molecules, School of Chemistry and Chemical Engineering, Shanghai Jiao Tong University, 800 Dongchuan Road, Shanghai, 200240, China.
School of Pharmacy, Shanghai Jiao Tong University, 800 Dongchuan Road, Shanghai, 200240, China.
Angew Chem Int Ed Engl. 2021 Jul 26;60(31):16989-16993. doi: 10.1002/anie.202106566. Epub 2021 Jun 24.
Asymmetric hydrogenation is one of the most powerful methods for the preparation of single enantiomer compounds. However, the chemo- and enantioselective hydrogenation of the relatively inert unsaturated group in substrates possessing multiple unsaturated bonds remains a challenge. We herein report a protocol for the highly chemo- and enantioselective hydrogenation of conjugated enynes while keeping the alkynyl bond intact. Mechanism studies indicate that the accompanying Zn generated from zinc reduction of the Co complex plays a critical role to initiate a plausible Co /Co catalytic cycle. This approach allows for the highly efficient generation of chiral propargylamines (up to 99.9 % ee and 2000 S/C) and further useful chemical transformations.
不对称氢化是制备单一对映体化合物最有力的方法之一。然而，对于具有多个不饱和键的底物中相对惰性的不饱和基团的化学选择性和对映选择性氢化仍然是一个挑战。本文报道了一种在保持炔键完整的情况下，对共轭烯炔进行高化学选择性和对映选择性氢化的方法。机理研究表明，Co 配合物还原锌生成的伴随 Zn 对引发合理的 Co/Co 催化循环起着关键作用。该方法可高效生成手性炔丙胺（高达 99.9%ee 和 2000 S/C），并进一步进行有用的化学转化。
