氟烷基取代环丙烯与氟烷基丙烯基硅烷作为羰基阳离子等价物的模块化合成

IF 19.6 1区 化学 Q1 CHEMISTRY, MULTIDISCIPLINARY
Chem Pub Date : 2025-09-03 DOI:10.1016/j.chempr.2025.102721
Gang Zhou, Yuan Yao, Xiaoqian He, Weilu Zhang, Shanshan Liu, Xiao Shen
{"title":"氟烷基取代环丙烯与氟烷基丙烯基硅烷作为羰基阳离子等价物的模块化合成","authors":"Gang Zhou, Yuan Yao, Xiaoqian He, Weilu Zhang, Shanshan Liu, Xiao Shen","doi":"10.1016/j.chempr.2025.102721","DOIUrl":null,"url":null,"abstract":"The carbynyl cation, which is a reactive species capable of forming three covalent bonds, remains relatively unexplored due to its extreme reactivity and the limited availability of efficient sources. Herein, we report the application of fluoroalkylacylsilanes as carbynyl cation equivalents, enabling the modular synthesis of fluoroalkyl-substituted cyclopropenes, where three new covalent bonds are constructed. The success of this reaction lies in the integration of sequential photocatalysis and acid catalysis in a one-pot process. Photocatalysis facilitates the carbene-mediated [2 + 1] cycloaddition with alkynes, while acid catalysis promotes formal C–O bond functionalization via cyclopropenium intermediates. Using this strategy, we have synthesized a diverse array of fluoroalkylated cyclopropenyl ethers, arenes, alkanes, thioethers, amines, and azides. These reactions are not only effective for the synthesis of simple cyclopropenes but also provide access to complex cyclopropenes that are otherwise challenging to prepare.","PeriodicalId":268,"journal":{"name":"Chem","volume":"45 1","pages":""},"PeriodicalIF":19.6000,"publicationDate":"2025-09-03","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":"0","resultStr":"{\"title\":\"Modular synthesis of fluoroalkyl-substituted cyclopropenes with fluoroalkylacylsilanes as carbynyl cation equivalents\",\"authors\":\"Gang Zhou, Yuan Yao, Xiaoqian He, Weilu Zhang, Shanshan Liu, Xiao Shen\",\"doi\":\"10.1016/j.chempr.2025.102721\",\"DOIUrl\":null,\"url\":null,\"abstract\":\"The carbynyl cation, which is a reactive species capable of forming three covalent bonds, remains relatively unexplored due to its extreme reactivity and the limited availability of efficient sources. Herein, we report the application of fluoroalkylacylsilanes as carbynyl cation equivalents, enabling the modular synthesis of fluoroalkyl-substituted cyclopropenes, where three new covalent bonds are constructed. The success of this reaction lies in the integration of sequential photocatalysis and acid catalysis in a one-pot process. Photocatalysis facilitates the carbene-mediated [2 + 1] cycloaddition with alkynes, while acid catalysis promotes formal C–O bond functionalization via cyclopropenium intermediates. Using this strategy, we have synthesized a diverse array of fluoroalkylated cyclopropenyl ethers, arenes, alkanes, thioethers, amines, and azides. These reactions are not only effective for the synthesis of simple cyclopropenes but also provide access to complex cyclopropenes that are otherwise challenging to prepare.\",\"PeriodicalId\":268,\"journal\":{\"name\":\"Chem\",\"volume\":\"45 1\",\"pages\":\"\"},\"PeriodicalIF\":19.6000,\"publicationDate\":\"2025-09-03\",\"publicationTypes\":\"Journal Article\",\"fieldsOfStudy\":null,\"isOpenAccess\":false,\"openAccessPdf\":\"\",\"citationCount\":\"0\",\"resultStr\":null,\"platform\":\"Semanticscholar\",\"paperid\":null,\"PeriodicalName\":\"Chem\",\"FirstCategoryId\":\"92\",\"ListUrlMain\":\"https://doi.org/10.1016/j.chempr.2025.102721\",\"RegionNum\":1,\"RegionCategory\":\"化学\",\"ArticlePicture\":[],\"TitleCN\":null,\"AbstractTextCN\":null,\"PMCID\":null,\"EPubDate\":\"\",\"PubModel\":\"\",\"JCR\":\"Q1\",\"JCRName\":\"CHEMISTRY, MULTIDISCIPLINARY\",\"Score\":null,\"Total\":0}","platform":"Semanticscholar","paperid":null,"PeriodicalName":"Chem","FirstCategoryId":"92","ListUrlMain":"https://doi.org/10.1016/j.chempr.2025.102721","RegionNum":1,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":null,"EPubDate":"","PubModel":"","JCR":"Q1","JCRName":"CHEMISTRY, MULTIDISCIPLINARY","Score":null,"Total":0}
引用次数: 0

摘要

羰基阳离子是一种能够形成三个共价键的反应性物质,由于其极强的反应性和有效来源的有限性,仍然相对未被开发。本文中,我们报道了氟烷基烷基硅烷作为羰基阳离子等价物的应用,使得氟烷基取代环丙烯的模块化合成成为可能,其中构建了三个新的共价键。该反应的成功之处在于将顺序光催化和酸催化在一锅过程中结合起来。光催化促进了碳介导的[2 + 1]与炔烃的环加成反应,而酸催化通过环丙烯中间体促进了正式的C-O键功能化。使用这种策略,我们已经合成了各种氟烷基化环丙烯醚、芳烃、烷烃、硫醚、胺和叠氮化物。这些反应不仅对简单环丙烯的合成有效,而且还提供了制备复杂环丙烯的途径,否则很难制备。
本文章由计算机程序翻译,如有差异,请以英文原文为准。

Modular synthesis of fluoroalkyl-substituted cyclopropenes with fluoroalkylacylsilanes as carbynyl cation equivalents

Modular synthesis of fluoroalkyl-substituted cyclopropenes with fluoroalkylacylsilanes as carbynyl cation equivalents
The carbynyl cation, which is a reactive species capable of forming three covalent bonds, remains relatively unexplored due to its extreme reactivity and the limited availability of efficient sources. Herein, we report the application of fluoroalkylacylsilanes as carbynyl cation equivalents, enabling the modular synthesis of fluoroalkyl-substituted cyclopropenes, where three new covalent bonds are constructed. The success of this reaction lies in the integration of sequential photocatalysis and acid catalysis in a one-pot process. Photocatalysis facilitates the carbene-mediated [2 + 1] cycloaddition with alkynes, while acid catalysis promotes formal C–O bond functionalization via cyclopropenium intermediates. Using this strategy, we have synthesized a diverse array of fluoroalkylated cyclopropenyl ethers, arenes, alkanes, thioethers, amines, and azides. These reactions are not only effective for the synthesis of simple cyclopropenes but also provide access to complex cyclopropenes that are otherwise challenging to prepare.
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
Chem
Chem Environmental Science-Environmental Chemistry
CiteScore
32.40
自引率
1.30%
发文量
281
期刊介绍: Chem, affiliated with Cell as its sister journal, serves as a platform for groundbreaking research and illustrates how fundamental inquiries in chemistry and its related fields can contribute to addressing future global challenges. It was established in 2016, and is currently edited by Robert Eagling.
×
引用
GB/T 7714-2015
复制
MLA
复制
APA
复制
导出至
BibTeX EndNote RefMan NoteFirst NoteExpress
×
提示
您的信息不完整,为了账户安全,请先补充。
现在去补充
×
提示
您因"违规操作"
具体请查看互助需知
我知道了
×
提示
确定
请完成安全验证×
copy
已复制链接
快去分享给好友吧!
我知道了
右上角分享
点击右上角分享
0
联系我们:info@booksci.cn Book学术提供免费学术资源搜索服务,方便国内外学者检索中英文文献。致力于提供最便捷和优质的服务体验。 Copyright © 2023 布克学术 All rights reserved.
京ICP备2023020795号-1
ghs 京公网安备 11010802042870号
Book学术文献互助
Book学术文献互助群
群 号:604180095
Book学术官方微信