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钴(III)催化的通过C-H官能化实现对映选择性分子间碳胺化反应

Cobalt(III)-Catalyzed Enantioselective Intermolecular Carboamination by C-H Functionalization.

作者信息

Ozols Kristers, Onodera Shunsuke, Woźniak Łukasz, Cramer Nicolai

机构信息

Institute of Chemical Sciences and Engineering (ISIC), EPFL SB ISIC LCSA, BCH 4305, 1015, Lausanne, Switzerland.

Department of Chemistry, Faculty of Science and Technology, Keio University, 3-14-1 Hiyoshi, Kohoku-ku, Yokohama, 223-8522, Japan.

出版信息

Angew Chem Int Ed Engl. 2021 Jan 11;60(2):655-659. doi: 10.1002/anie.202011140. Epub 2020 Nov 10.

Abstract

High-valent cyclopentadienyl cobalt catalysis is a versatile tool for sustainable C-H bond functionalizations. To harness the full potential of this strategy, control of the stereoselectivity of these processes is necessary. Herein, we report highly enantioselective intermolecular carboaminations of alkenes through C-H activation of N-phenoxyamides catalyzed by Co -complexes equipped with chiral cyclopentadienyl (Cp ) ligands. The method converts widely available acrylates as well as bicyclic olefins into attractive enantioenriched isotyrosine derivatives as well as elaborated amino-substituted bicyclic scaffolds under very mild conditions. The outlined reactivity is unique to the Cp Co complexes and is complementary to the reactivity of 4d- and 5d- precious-metal catalysts.

摘要

高价环戊二烯基钴催化是实现可持续C-H键官能团化的一种通用工具。为了充分发挥这一策略的潜力,控制这些反应过程的立体选择性是必要的。在此,我们报道了通过手性环戊二烯基(Cp)配体的钴配合物催化N-苯氧基酰胺的C-H活化实现烯烃的高度对映选择性分子间碳胺化反应。该方法能在非常温和的条件下,将广泛可得的丙烯酸酯以及双环烯烃转化为具有吸引力的对映体富集异酪氨酸衍生物以及复杂的氨基取代双环骨架。所概述的反应活性是Cp钴配合物所特有的,并且与4d和5d贵金属催化剂的反应活性互补。

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