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催化作用:利用高通量机械化学方法开发在有氧条件下耐受性增强的溶剂用量最少的芳基胺化反应和C(sp²)-C(sp³)交叉偶联反应。

Catalysis: Utilizing Increased Throughput Mechanochemistry to Develop Solvent-Minimized Aryl Amination and C(sp2)-C(sp3) Cross-Coupling Reactions with Increased Tolerance to Aerobic Conditions.

作者信息

Millward Francis, Zysman-Colman Eli

机构信息

Organic Semiconductor Centre, EaStCHEM School of Chemistry, University of St Andrews, St Andrews KY16 9ST, U.K.

出版信息

J Am Chem Soc. 2025 Jul 2;147(26):22919-22931. doi: 10.1021/jacs.5c05503. Epub 2025 May 22.

Abstract

Photocatalysis as a tool used in organic synthesis has predominantly relied on the use of solvents, be it under homogeneous or heterogeneous conditions. In particular, metallaphotoredox catalysis reactions commonly use toxic organic solvents such as DMA and DMF. Herein, we demonstrate how mechanophotocatalysis, the synergistic union of mechanochemistry and photocatalysis, is compatible with this class of dual catalysis reactions involving both photocatalyst and nickel(II) cocatalysts. Using ball milling, these mechanistically complex reactions can be conducted in the absence of a bulk solvent and under air, affording high-yielding aryl aminations and C(sp2)-C(sp3) cross-couplings with alkyl carboxylic acids, alkyl trifluoroborate salts, and alkyl bromides. These advances are facilitated by the introduction of a novel reaction vessel design for conducting four mechanophotocatalysis reactions simultaneously. This work highlights the promise of solvent-minimized photocatalysis reactions, demonstrating that in these examples bulk solvent is redundant, thus significantly reducing this waste stream. Through time-resolved photoluminescence studies, we observed that the excited states of five different photocatalysts were quenched by oxygen more significantly in solution than in the solid state, providing evidence for the origin of the increased tolerance to aerobic conditions that these mechanophotocatalysis reactions experience.

摘要

光催化作为有机合成中使用的一种工具,主要依赖于溶剂的使用,无论是在均相还是非均相条件下。特别是,金属光氧化还原催化反应通常使用有毒的有机溶剂,如N,N-二甲基乙酰胺(DMA)和N,N-二甲基甲酰胺(DMF)。在此,我们展示了机械光催化,即机械化学与光催化的协同结合,如何与这类涉及光催化剂和镍(II)共催化剂的双催化反应兼容。通过球磨,这些机理复杂的反应可以在无大量溶剂且在空气中进行,从而实现高产率的芳基胺化反应以及与烷基羧酸、烷基三氟硼酸盐和烷基溴的C(sp²)-C(sp³)交叉偶联反应。一种用于同时进行四个机械光催化反应的新型反应容器设计推动了这些进展。这项工作突出了溶剂用量最少的光催化反应的前景,表明在这些实例中大量溶剂是多余的,从而显著减少了这一废物流。通过时间分辨光致发光研究,我们观察到五种不同光催化剂的激发态在溶液中比在固态中更易被氧气猝灭,这为这些机械光催化反应对有氧条件耐受性增加的原因提供了证据。

https://cdn.ncbi.nlm.nih.gov/pmc/blobs/cf20/12232315/4df8c71c070e/ja5c05503_0001.jpg

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