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钴/萨洛克斯催化的芳基膦酰胺的对映选择性 C-H 官能化。

Cobalt/Salox-Catalyzed Enantioselective C-H Functionalization of Arylphosphinamides.

机构信息

Center of Chemistry for Frontier Technologies, Department of Chemistry, Zhejiang University, Hangzhou, 310027, China.

出版信息

Angew Chem Int Ed Engl. 2022 Jun 20;61(25):e202202892. doi: 10.1002/anie.202202892. Epub 2022 Apr 21.

Abstract

Previous methods on Co -catalyzed asymmetric C-H activation rely on the use of tailor-made cyclopentadienyl-ligated Co complexes, which require lengthy steps for the preparation. Herein, we report an unprecedented enantioselective C-H functionalization enabled by a simple cobalt/salicyloxazoline (Salox) catalysis. The chiral Salox ligands can be easily prepared in one step from salicylonitrile and chiral amino alcohols. A broad range of P-stereogenic compounds were synthesized in high yields with excellent enantioselectivities (45 examples, up to 99 % yield and >99 % ee). The isolation and characterization of several intermediates provided insights into the generation of active catalytic cobalt species, the action of Salox, and the mode of stereocontrol.

摘要

先前的偕金属催化不对称 C-H 活化方法依赖于使用定制的茂基配位钴配合物,这需要经过冗长的步骤来制备。在此,我们报道了一种前所未有的通过简单的钴/水杨醛亚胺(Salox)催化实现的对映选择性 C-H 官能化。手性 Salox 配体可以通过水杨醛腈和手性氨基醇一步轻松制备。一系列 P-手性化合物以高产率和优异的对映选择性(45 个实例,最高产率为 99%,对映体过量值大于 99%)合成。对几个中间体的分离和表征提供了对活性催化钴物种的生成、Salox 的作用以及立体控制模式的深入了解。

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