{"title":"Regulating the Acidity of HF/Pyridine Media to Control the Chemodivergent Fluoro- and Hydro-Heteroalkylation of Olefins","authors":"Mélissa Longuet, Fabien Naullet, Alexandre Pérochon, Agnès Martin-Mingot, Frédéric Guégan*, Bastien Michelet* and Sébastien Thibaudeau*, ","doi":"10.1021/jacs.5c07526","DOIUrl":null,"url":null,"abstract":"<p >Oxocarbenium ions are important reactive intermediates with many applications in organic synthesis. Among them, primary oxocarbenium ions have been much less explored, in part due to the difficulty of controlling their reactivity under standard conditions. Here, we show that the reactivity of such species can be finely modulated in strongly acidic HF/pyridine media. By leveraging the tunable acidity of HF/pyridine solutions, their reaction with olefins can be diverted toward either fluoro- or hydro-oxyalkylation. Additional spectroscopic and computational investigations provide insights into the mechanism.</p>","PeriodicalId":49,"journal":{"name":"Journal of the American Chemical Society","volume":"147 32","pages":"29079–29087"},"PeriodicalIF":15.6000,"publicationDate":"2025-08-01","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":"0","resultStr":null,"platform":"Semanticscholar","paperid":null,"PeriodicalName":"Journal of the American Chemical Society","FirstCategoryId":"92","ListUrlMain":"https://pubs.acs.org/doi/10.1021/jacs.5c07526","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
Abstract
Oxocarbenium ions are important reactive intermediates with many applications in organic synthesis. Among them, primary oxocarbenium ions have been much less explored, in part due to the difficulty of controlling their reactivity under standard conditions. Here, we show that the reactivity of such species can be finely modulated in strongly acidic HF/pyridine media. By leveraging the tunable acidity of HF/pyridine solutions, their reaction with olefins can be diverted toward either fluoro- or hydro-oxyalkylation. Additional spectroscopic and computational investigations provide insights into the mechanism.
期刊介绍:
The flagship journal of the American Chemical Society, known as the Journal of the American Chemical Society (JACS), has been a prestigious publication since its establishment in 1879. It holds a preeminent position in the field of chemistry and related interdisciplinary sciences. JACS is committed to disseminating cutting-edge research papers, covering a wide range of topics, and encompasses approximately 19,000 pages of Articles, Communications, and Perspectives annually. With a weekly publication frequency, JACS plays a vital role in advancing the field of chemistry by providing essential research.