光电化学镍催化的具有未活化 C/Si-H 键的烯烃的羧基化/硅烷酰化反应

IF 9.2 1区 化学 Q1 CHEMISTRY, MULTIDISCIPLINARY
Green Chemistry Pub Date : 2024-07-15 DOI:10.1039/d3gc04109c
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引用次数: 0

摘要

在烯烃的不饱和键上直接和选择性地安装两个不同的官能团是有机合成的一个长期目标。在此,我们首次报道了一种通过 LMCT 工艺,用未活化的烷烃/氢硅烷对烯进行羧基化/硅烷酰化的光电化学方法。该方法以经济、可持续的方式,从市场上可买到的材料中快速获得了大量复杂多样的酮。此外,该方案还可放大到克级。这种配对电催化策略具有优异的区域选择性和广泛的底物范围,不需要外部氧化剂,而且资源经济性高。为了确定这些转化过程中光电化学镍(I)/镍(II)/镍(III)循环的优先途径,我们进行了一系列机理实验。
本文章由计算机程序翻译,如有差异,请以英文原文为准。

Photoelectrochemical nickel-catalyzed carboacylation/silanoylation of alkenes with unactivated C/Si–H bonds†

Photoelectrochemical nickel-catalyzed carboacylation/silanoylation of alkenes with unactivated C/Si–H bonds†

Photoelectrochemical nickel-catalyzed carboacylation/silanoylation of alkenes with unactivated C/Si–H bonds†

Direct and selective installation of two different functional groups into the unsaturated bonds of alkenes constitutes a long-standing goal in organic synthesis. Herein, we first report a photoelectrochemical approach for the carboacylation/silanoylation of alkenes with unactivated alkanes/hydrosilanes via the LMCT process. A number of ketones with high complexity and diversity were rapidly obtained from commercially available materials in an economical and sustainable manner. Furthermore, this protocol can be scaled up to the gram-level. This paired electrocatalysis strategy features excellent regioselectivity, and ample substrate scope, is external-oxidant-free, and features a high resource economy. A series of mechanistic experiments were performed to determine the preferred pathway for the photoelectrochemical Ni(i)/Ni(ii)/Ni(iii) cycles in these transformations.

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来源期刊
Green Chemistry
Green Chemistry 化学-化学综合
CiteScore
16.10
自引率
7.10%
发文量
677
审稿时长
1.4 months
期刊介绍: Green Chemistry is a journal that provides a unique forum for the publication of innovative research on the development of alternative green and sustainable technologies. The scope of Green Chemistry is based on the definition proposed by Anastas and Warner (Green Chemistry: Theory and Practice, P T Anastas and J C Warner, Oxford University Press, Oxford, 1998), which defines green chemistry as the utilisation of a set of principles that reduces or eliminates the use or generation of hazardous substances in the design, manufacture and application of chemical products. Green Chemistry aims to reduce the environmental impact of the chemical enterprise by developing a technology base that is inherently non-toxic to living things and the environment. The journal welcomes submissions on all aspects of research relating to this endeavor and publishes original and significant cutting-edge research that is likely to be of wide general appeal. For a work to be published, it must present a significant advance in green chemistry, including a comparison with existing methods and a demonstration of advantages over those methods.
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