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对映选择性电还原炔烃-醛偶联反应

Enantioselective electroreductive alkyne-aldehyde coupling.

作者信息

Cao Xiyang, Fu Yuyang, Tao Yongsheng, Lu Qingquan

机构信息

The Institute for Advanced Studies, Wuhan University, Wuhan, Hubei, P. R. China.

Wuhan University Shenzhen Research Institute, Shenzhen, P. R. China.

出版信息

Nat Commun. 2025 Jul 1;16(1):5686. doi: 10.1038/s41467-025-60230-5.

DOI:10.1038/s41467-025-60230-5
PMID:40592859
原文链接:https://pmc.ncbi.nlm.nih.gov/articles/PMC12219297/
Abstract

Electrocatalytic methods that facilitate the asymmetric reductive coupling of two π-components with complete control over regio-, stereo-, and enantioselectivity remain underexplored. Herein, we report a highly regio- and enantioselective cobaltaelectro-catalyzed alkyne-aldehyde coupling reaction, in which protons and electrons serve as the hydrogen source and reductant, respectively. Earth-abundant cobalt and air-stable (S,S)-2,3-bis(tert-butylmethylphosphino)quinoxaline (QuinoxP*) are used as the catalyst and ligand, respectively. A series of enantioenriched allylic alcohols can be constructed with excellent regio- (>19:1), stereo- (>19:1 E:Z), and enantioselectivity (up to 98% ee).

摘要

能够完全控制区域选择性、立体选择性和对映选择性,促进两个π组分进行不对称还原偶联的电催化方法仍未得到充分探索。在此,我们报道了一种高度区域选择性和对映选择性的钴电催化炔烃-醛偶联反应,其中质子和电子分别作为氢源和还原剂。储量丰富的钴和空气稳定的(S,S)-2,3-双(叔丁基甲基膦基)喹喔啉(QuinoxP*)分别用作催化剂和配体。一系列对映体富集的烯丙醇能够以优异的区域选择性(>19:1)、立体选择性(>19:1 E:Z)和对映选择性(高达98% ee)构建而成。

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本文引用的文献

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Chemodivergent, enantio- and regioselective couplings of alkynes, aldehydes and silanes enabled by nickel/N-heterocyclic carbene catalysis.镍/氮杂环卡宾催化实现的炔烃、醛和硅烷的化学发散、对映和区域选择性偶联反应。
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钴催化下腈与胺的电氢化反应
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Highly Regio- and Enantioselective Reductive Coupling of Alkynes and Aldehydes via Photoredox Cobalt Dual Catalysis.通过光氧化还原钴双催化实现炔烃和醛的高区域和对映选择性还原偶联。
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