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钴催化二芳基酮与基于二茂铁的二级氧化膦配体的对映选择性氢化反应

Cobalt-Catalyzed Enantioselective Hydrogenation of Diaryl Ketones with Ferrocene-Based Secondary Phosphine Oxide Ligands.

作者信息

Zeng Liyao, Zhao Menglong, Lin Bijin, Song Jingyuan, Tucker James H R, Wen Jialin, Zhang Xumu

机构信息

Department of Chemistry, Guangdong Provincial Key Laboratory of Catalysis, Southern University of Science and Technology, 1088 Xueyuan Road, Shenzhen 518055, China.

School of Chemistry, University of Birmingham, Edgbaston, Birmingham B15 2TT, U.K.

出版信息

Org Lett. 2023 Aug 25;25(33):6228-6233. doi: 10.1021/acs.orglett.3c02530. Epub 2023 Aug 16.

Abstract

A new class of cobalt catalytic system for asymmetric hydrogenation of ketones was herein reported, involving the development of novel ferrocene-based secondary phosphine oxide ligands. An unusual P-O bidentate coordination pattern with cobalt was confirmed by an X-ray diffraction study. The bichelating tetrahedral cobalt(II) complexes afforded high reactivities (up to 99% yield) and good to excellent enantioselectivities (up to 92% ee) in the AH of various -substituted diaryl ketones. In addition, the diferrocenyl cobalt complex was characterized with intriguing UV-vis absorption and electrochemical properties.

摘要

本文报道了一类用于酮不对称氢化的新型钴催化体系,其中涉及新型二茂铁基二膦氧化物配体的开发。通过X射线衍射研究证实了与钴形成的一种不寻常的P-O双齿配位模式。双螯合四面体钴(II)配合物在各种α-取代二芳基酮的不对称氢化反应中表现出高反应活性(产率高达99%)和良好至优异的对映选择性(对映体过量高达92%)。此外,二茂铁基钴配合物具有引人注目的紫外可见吸收和电化学性质。

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