Photocatalyzed Defluorinative Dichloromethylation of α-CF3 Alkenes Using CHCl3 as the Radical Source,The Journal of Organic Chemistry

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Photocatalyzed Defluorinative Dichloromethylation of α-CF3 Alkenes Using CHCl3 as the Radical Source
The Journal of Organic Chemistry ( IF 3.3 ) Pub Date : 2022-06-18 , DOI: 10.1021/acs.joc.2c01106
Mei-Chun Wu _{1,

2} , Yi-Xuan Chen ₁ , Ming-Zhi Li ₁ , Jun-An Xiao ₃ , Zhi-Peng Ye ₁ , Jian-Ping Guan ₁ , Hao-Yue Xiang ₁ , Kai Chen ₁ , Hua Yang ₁

Affiliation

A visible-light-induced defluorinative dichloromethylation of α-CF₃ alkenes was developed with cheap and readily accessible chloroform simultaneously as a dichloromethylation reagent and reaction medium, leading to the facile preparation of new polyhalogenated scaffolds. Notably, the change from CHCl₃ to CDCl₃ offers a straightforward pathway for accessing the deuterated analogues with excellent degrees of D incorporation. Mechanistic studies suggested the reaction underwent a radical addition of the dichloromethyl radical with alkenes, followed by sequential single-electron transfer and defluorination. This protocol features mild conditions, easy operation, facile scalability, and high efficiency, allowing convenient access to dichloronated gem-difluoroalkenes.

中文翻译：

以 CHCl3 为自由基源的 α-CF3 烯烃的光催化脱氟二氯甲基化

使用廉价且易于获得的氯仿同时作为二氯甲基化试剂和反应介质开发了可见光诱导的α-CF ₃烯烃脱氟二氯甲基化，从而轻松制备了新的多卤化支架。_{值得注意的是，从 CHCl 3}到 CDCl _{3 的}变化为获取具有出色 D 掺入度的氘代类似物提供了一条直接的途径。机理研究表明，该反应经历了二氯甲基自由基与烯烃的自由基加成，然后是连续的单电子转移和脱氟。该协议条件温和、操作简单、可扩展性强、效率高，可方便地获取二氯宝石-二氟烯烃。

更新日期：2022-06-18

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