Nickel-Catalyzed Atroposelective Carbo-Carboxylation of Alkynes with CO2: En Route to Axially Chiral Carboxylic Acids.

IF 16.1 1区 化学 Q1 CHEMISTRY, MULTIDISCIPLINARY
Chao Li, Xiao-Wang Chen, Li-Li Liao, Yong-Yuan Gui, Jing-Wei Yang, Shuo Zhang, Jun-Ping Yue, Xiangge Zhou, Jian-Heng Ye, Yu Lan, Da-Gang Yu
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引用次数: 0

Abstract

Precise synthesis of carboxylic acids via catalytic carboxylation with CO2 is highly appealing. Although considerable advancements have been achieved in difunctionalizing carboxylation of unsaturated hydrocarbons, the asymmetric variants are conspicuously underdeveloped, particularly in addressing axially chiral alkenes. Herein, we report the first catalytic atroposelective carboxylation of alkynes with CO2. A variety of valuable axially chiral carboxylic acids are obtained with good yields and high chemo-, regio-, E/Z and enantio-selectivities. Notably, an unexpected anti-selective carbo-carboxylation is observed in the sp2-hybrid carbo-electrophile-initiated reductive carboxylation of alkynes. Mechanistic studies including DFT calculation elucidate the origin of chiral induction and anti-selectivity in vinyl-carboxylation of alkynes.

镍催化的炔烃与 CO2 的无选择性羧化反应:获得轴向手性羧酸的途径。
通过二氧化碳催化羧化作用精确合成羧酸非常有吸引力。尽管在不饱和烃的双官能团化羧化方面已经取得了相当大的进展,但不对称变体的研究却明显不足,尤其是在处理轴向手性烯烃方面。在此,我们首次报告了炔烃与 CO2 的催化反选择性羧化反应。我们以良好的产率和较高的化学、区域、E/Z 和对映选择性获得了多种有价值的轴向手性羧酸。值得注意的是,在炔烃的 sp2-杂化羧基-亲电体引发的还原羧化反应中,观察到了意想不到的反选择性羧化。包括 DFT 计算在内的机理研究阐明了炔烃乙烯基羧化中手性诱导和反选择性的起源。
本文章由计算机程序翻译,如有差异,请以英文原文为准。
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来源期刊
CiteScore
26.60
自引率
6.60%
发文量
3549
审稿时长
1.5 months
期刊介绍: Angewandte Chemie, a journal of the German Chemical Society (GDCh), maintains a leading position among scholarly journals in general chemistry with an impressive Impact Factor of 16.6 (2022 Journal Citation Reports, Clarivate, 2023). Published weekly in a reader-friendly format, it features new articles almost every day. Established in 1887, Angewandte Chemie is a prominent chemistry journal, offering a dynamic blend of Review-type articles, Highlights, Communications, and Research Articles on a weekly basis, making it unique in the field.
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