Shenzhen Grubbs Institute, Department of Chemistry, Guangdong Provincial Key Laboratory of Catalysis, Southern University of Science and Technology, Shenzhen, 518055, Guangdong, P. R. China.
Angew Chem Int Ed Engl. 2021 Jan 18;60(3):1599-1604. doi: 10.1002/anie.202011339. Epub 2020 Nov 9.
The development of enantioselective alkyl-alkyl cross-couplings with coinstantaneous formation of a stereogenic center without the use of sensitive organometallic species is attractive yet challenging. Herein, we report the intermolecular regio- and enantioselective formal hydrofunctionalizations of acrylamides, forging a stereogenic center α-position to the newly formed C -C bond for the first time. The use of a newly developed chiral ligand enables the electronically-reversed formal hydrofunctionalizations, including hydroalkylation, hydrobenzylation, and hydropropargylation, offering an efficient way to access diverse enantioenriched amides with a tertiary α-stereogenic carbon center which is facile to racemize. This operationally simple protocol allows for the anti-Markovnikov enantioselective hydroalkylation, and unprecedented hydrobenzylation, hydropropargylation under mild conditions with excellent functional group compatibility, delivering a wide range of amides with excellent levels of enantioselectivity.
具有对映选择性的烷基-烷基交叉偶联反应，同时在不使用敏感有机金属物种的情况下形成手性中心，这是吸引人但具有挑战性的。在此，我们首次报道了酰胺的分子间区域和对映选择性形式氢官能化反应，在新形成的 C-C 键的 α-位构建手性中心。使用新开发的手性配体，可以进行电子反转的形式氢官能化反应，包括氢烷基化、氢苄基化和氢炔丙基化，为获得具有易于外消旋化的三级 α-手性碳原子的各种对映体富集酰胺提供了一种有效方法。该操作简单的方案允许在温和条件下进行反 Markovnikov 对映选择性氢烷基化反应，以及前所未有的氢苄基化反应和氢炔丙基化反应，具有出色的官能团兼容性，可获得具有优异对映选择性的广泛酰胺。
