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锰催化未活化烯烃的氢芳基化反应

Manganese-Catalyzed Hydroarylation of Unactivated Alkenes.

作者信息

Liu Ting, Yang Yunhui, Wang Congyang

机构信息

Beijing National Laboratory for Molecular Sciences, CAS key Laboratory of Molecular Recognition and Function, CAS Research/Education Center for Excellence in Molecular Sciences, Institute of Chemistry, Chinese Academy of Sciences, Beijing, 100190, China.

University of Chinese Academy of Sciences, Beijing, 100049, China.

出版信息

Angew Chem Int Ed Engl. 2020 Aug 17;59(34):14256-14260. doi: 10.1002/anie.202003830. Epub 2020 Jul 6.

Abstract

Transition-metal-catalyzed hydroarylation of unactivated alkenes with strategic use of remote coordinating functional groups has received significant attention recently to address the issues of both low reactivity and poor selectivity. The bidentate 8-aminoquinoline amide group is the most successfully adopted in unactivated alkenes for Pd and Ni catalysis. We describe the first manganese-catalyzed hydroarylation of unactivated alkenes bearing diverse simple functionalities with arylboronic acids. A series of δ- and γ-arylated amides, ketones, pyridines, and amines was accessed with excellent regioselectivity and in high yields. Hydroalkenylation of unactivated alkenes was also shown to be applicable under this manganese-catalysis regime. The method features earth-abundant manganese catalysis, easily available substrates, broad functional-group tolerance, and excellent regioselective control.

摘要

通过策略性地使用远程配位官能团实现的过渡金属催化未活化烯烃的氢芳基化反应,近来因要解决低反应活性和低选择性问题而受到了广泛关注。双齿8-氨基喹啉酰胺基团在未活化烯烃的钯和镍催化反应中是应用最为成功的。我们报道了首例锰催化带有各种简单官能团的未活化烯烃与芳基硼酸的氢芳基化反应。一系列具有优异区域选择性和高产率的δ-和γ-芳基化酰胺、酮、吡啶和胺得以合成。未活化烯烃的氢烯基化反应在这种锰催化体系下也被证明是可行的。该方法具有以储量丰富的锰为催化剂、底物易于获得、官能团耐受性广以及出色的区域选择性控制等特点。

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