钯通过hiyama型偶联催化烯丙基宝石二氟化物的氰化和烷基化

IF 4.2 2区化学 Q2 CHEMISTRY, MULTIDISCIPLINARY

Chemical Communications Pub Date : 2025-09-29 DOI:10.1039/d5cc05064b

Jia-Chen Miao, Lu-ning Tang, Yi-Bin Wang, Xianqiang Kong, Ming Chen

{"title":"钯通过hiyama型偶联催化烯丙基宝石二氟化物的氰化和烷基化","authors":"Jia-Chen Miao, Lu-ning Tang, Yi-Bin Wang, Xianqiang Kong, Ming Chen","doi":"10.1039/d5cc05064b","DOIUrl":null,"url":null,"abstract":"Wereport a palladium-catalyzed, Hiyama-type defluorinative cross-coupling of allylic gem-difluorides with trimethylsilyl cyanide and silylalkynes via selective C-F bond activation. The transformation proceeds through a tandem sequence of oxidative addition, Si-F-assisted transmetalation, and reductive elimination, enabling efficient construction of C(sp³)-CN and C(sp³)-C(sp) bonds under base-and additive-free conditions. The reaction exhibits broad substrate scope, excellent functional group tolerance, and high regio-and Z-selectivity, affording structurally diverse monofluorinated alkenes in good to excellent yields. Furthermore, the resulting fluoroalkenes serve as versatile intermediates for downstream functionalization, underscoring the synthetic utility of this Si-F-driven cross-coupling platform.","PeriodicalId":67,"journal":{"name":"Chemical Communications","volume":"32 1","pages":""},"PeriodicalIF":4.2000,"publicationDate":"2025-09-29","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":"0","resultStr":"{\"title\":\"Palladium-Catalyzed Cyanation and Alkynylation of Allylic gem-Difluorides via Hiyama-Type Coupling\",\"authors\":\"Jia-Chen Miao, Lu-ning Tang, Yi-Bin Wang, Xianqiang Kong, Ming Chen\",\"doi\":\"10.1039/d5cc05064b\",\"DOIUrl\":null,\"url\":null,\"abstract\":\"Wereport a palladium-catalyzed, Hiyama-type defluorinative cross-coupling of allylic gem-difluorides with trimethylsilyl cyanide and silylalkynes via selective C-F bond activation. The transformation proceeds through a tandem sequence of oxidative addition, Si-F-assisted transmetalation, and reductive elimination, enabling efficient construction of C(sp³)-CN and C(sp³)-C(sp) bonds under base-and additive-free conditions. The reaction exhibits broad substrate scope, excellent functional group tolerance, and high regio-and Z-selectivity, affording structurally diverse monofluorinated alkenes in good to excellent yields. Furthermore, the resulting fluoroalkenes serve as versatile intermediates for downstream functionalization, underscoring the synthetic utility of this Si-F-driven cross-coupling platform.\",\"PeriodicalId\":67,\"journal\":{\"name\":\"Chemical Communications\",\"volume\":\"32 1\",\"pages\":\"\"},\"PeriodicalIF\":4.2000,\"publicationDate\":\"2025-09-29\",\"publicationTypes\":\"Journal Article\",\"fieldsOfStudy\":null,\"isOpenAccess\":false,\"openAccessPdf\":\"\",\"citationCount\":\"0\",\"resultStr\":null,\"platform\":\"Semanticscholar\",\"paperid\":null,\"PeriodicalName\":\"Chemical Communications\",\"FirstCategoryId\":\"92\",\"ListUrlMain\":\"https://doi.org/10.1039/d5cc05064b\",\"RegionNum\":2,\"RegionCategory\":\"化学\",\"ArticlePicture\":[],\"TitleCN\":null,\"AbstractTextCN\":null,\"PMCID\":null,\"EPubDate\":\"\",\"PubModel\":\"\",\"JCR\":\"Q2\",\"JCRName\":\"CHEMISTRY, MULTIDISCIPLINARY\",\"Score\":null,\"Total\":0}","platform":"Semanticscholar","paperid":null,"PeriodicalName":"Chemical Communications","FirstCategoryId":"92","ListUrlMain":"https://doi.org/10.1039/d5cc05064b","RegionNum":2,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":null,"EPubDate":"","PubModel":"","JCR":"Q2","JCRName":"CHEMISTRY, MULTIDISCIPLINARY","Score":null,"Total":0}

引用次数: 0

摘要

本研究通过选择性C-F键激活，钯催化的烯丙基宝石二氟化物与三甲基硅基氰化物和硅基炔的hiyama型脱氟交叉偶联。转化通过氧化加成、si -f辅助金属转化和还原消除的串联序列进行，从而在无碱和无添加剂的条件下有效地构建C（sp³）-CN和C（sp³）-C（sp）键。该反应具有广泛的底物范围、优异的官能团耐受性、高的区域选择性和z选择性，可生产出结构多样的单氟烯烃，收率很高。此外，所得到的氟烯烃作为下游功能化的多功能中间体，强调了这种si - f驱动的交叉耦合平台的合成效用。

本文章由计算机程序翻译，如有差异，请以英文原文为准。

查看原文本刊更多论文

Palladium-Catalyzed Cyanation and Alkynylation of Allylic gem-Difluorides via Hiyama-Type Coupling

Wereport a palladium-catalyzed, Hiyama-type defluorinative cross-coupling of allylic gem-difluorides with trimethylsilyl cyanide and silylalkynes via selective C-F bond activation. The transformation proceeds through a tandem sequence of oxidative addition, Si-F-assisted transmetalation, and reductive elimination, enabling efficient construction of C(sp³)-CN and C(sp³)-C(sp) bonds under base-and additive-free conditions. The reaction exhibits broad substrate scope, excellent functional group tolerance, and high regio-and Z-selectivity, affording structurally diverse monofluorinated alkenes in good to excellent yields. Furthermore, the resulting fluoroalkenes serve as versatile intermediates for downstream functionalization, underscoring the synthetic utility of this Si-F-driven cross-coupling platform.

求助全文

通过发布文献求助，成功后即可免费获取论文全文。去求助

来源期刊

Chemical Communications 化学-化学综合

CiteScore

8.60

自引率

4.10%

发文量

2705

审稿时长

1.4 months

期刊介绍： ChemComm (Chemical Communications) is renowned as the fastest publisher of articles providing information on new avenues of research, drawn from all the world''s major areas of chemical research.