双配体开启基于铁和含卤羧酸盐的光催化技术，用于烯烃的氯/氟-多卤烷基化反应

IF 7.6 1区化学 Q1 CHEMISTRY, MULTIDISCIPLINARY

Chemical Science Pub Date : 2024-11-04 DOI:10.1039/d4sc04038d

Wanru Han, Zhenyan Zhao, Kui Jiang, Yu Lan, Xuehan Yu, Xiaoyu Jiang, Wei Yang, Donghui Wei, Shi-Jun Li, Linbin Niu

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引用次数: 0

摘要

在此，我们展示了一种实用的双配体铁光催化范例--将各种含卤素的羧酸盐（CnXmCOO-，X：F、Cl、Br）转化为 CnXm 自由基，以易于获得的三氯乙腈/Selectfluor 作为亲电卤化试剂，对非活化烯烃进行有价值的氯/氟-多卤烷基化反应。详细的机理研究证明，利用两种配体--OMe/CF3--取代的联吡啶和乙腈/三氯乙腈，可以模块化地在原位组装出有效的铁基和 CnXmCOO 基光收集物种。后期修饰、低铁负载量（TON：257）和可行的克级合成都显示了该方案的实用性。因此，我们预计双配体铁光催化范例可能具有活化和转化惰性大宗化学品的能力。

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Dual Ligands Unlocking Iron and Halogen-Containing Carboxylates-based Photocatalysis for Chloro/Fluoro-Polyhaloalkylation of Alkenes

Herein, we demonstrate a practical dual ligand-enabled iron photocatalysis paradigm—translating all kinds of halogen-containing carboxylates (CnXmCOO−, X: F, Cl, Br) into CnXm radicals for the valuable chloro/fluoro-polyhaloalkylation of non-activated alkenes with easily available trichloroacetonitrile/Selectfluor as the electrophilic halogenation reagent. The modularly in-situ assembly of the effective iron and CnXmCOO−-based light-harvesting species using the two ligands—OMe/CF3-substituted bipyridine and acetonitrile/trichloroacetonitrile is evidenced by detailed mechanistic studies. The late-stage modification, low loading amount of iron (TON: 257) and feasible gram-scale synthesis show the utility of this protocol. We thus anticipate that the dual ligand-enabled iron photocatalysis paradigm may have an aptitude for activation and transformation of inert bulk chemicals.

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来源期刊

Chemical Science CHEMISTRY, MULTIDISCIPLINARY-

CiteScore

14.40

自引率

4.80%

发文量

1352

审稿时长

2.1 months

期刊介绍： Chemical Science is a journal that encompasses various disciplines within the chemical sciences. Its scope includes publishing ground-breaking research with significant implications for its respective field, as well as appealing to a wider audience in related areas. To be considered for publication, articles must showcase innovative and original advances in their field of study and be presented in a manner that is understandable to scientists from diverse backgrounds. However, the journal generally does not publish highly specialized research.