{"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}
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.
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.