Synthesis of Arenesulfenyl Fluorides and Fluorosulfenylation of Alkenes, Alkynes, and α-Diazocarbonyl Compounds

IF 16.1 1区 化学 Q1 CHEMISTRY, MULTIDISCIPLINARY
Nathan H. Faialaga, Dana P. Gephart, Breno D. Silva, Richard Y. Liu
{"title":"Synthesis of Arenesulfenyl Fluorides and Fluorosulfenylation of Alkenes, Alkynes, and α-Diazocarbonyl Compounds","authors":"Nathan H. Faialaga,&nbsp;Dana P. Gephart,&nbsp;Breno D. Silva,&nbsp;Richard Y. Liu","doi":"10.1002/anie.202422120","DOIUrl":null,"url":null,"abstract":"<p>Sulfenyl fluorides are organic compounds of sulfur in formal oxidation state +2 with the formula R−S−F. Although the chloride, bromide, and iodide analogues have been extensively described in the literature, arenesulfenyl fluorides remain essentially unstudied. These structures have been implicated as putative intermediates in established processes to access polyfluorinated sulfur species; however, definitive and direct evidence of their existence has not been obtained, nor has a systematic understanding of their reactivity. Here, we report the synthesis, isolation, and spectroscopic characterization of several arenesulfenyl fluorides, including structural analysis of 2,4-dinitrobenzenesulfenyl fluoride and 4-cyano-2-nitrobenzenesulfenyl fluoride by single-crystal X-ray diffraction. The functional group undergoes direct, efficient, and highly regioselective <i>anti</i>-addition to alkenes and alkynes, as well as insertion by carbenes. The resulting α- or β-fluoro thioether adducts can be readily transformed into useful fluorinated motifs, for example by modification of the sulfur groups (to sulfonamides or sulfonyl fluorides), by sulfur elimination (to generate formal C−H fluorination products), or by Julia–Kocienski olefination (to form vinyl fluorides). Thus, we establish that sulfenyl fluorides are unexpectedly accessible and stable compounds, which serve as versatile reagents for the production of fluorinated organic compounds.</p>","PeriodicalId":125,"journal":{"name":"Angewandte Chemie International Edition","volume":"64 12","pages":""},"PeriodicalIF":16.1000,"publicationDate":"2024-12-13","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":"0","resultStr":null,"platform":"Semanticscholar","paperid":null,"PeriodicalName":"Angewandte Chemie International Edition","FirstCategoryId":"92","ListUrlMain":"https://onlinelibrary.wiley.com/doi/10.1002/anie.202422120","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

Sulfenyl fluorides are organic compounds of sulfur in formal oxidation state +2 with the formula R−S−F. Although the chloride, bromide, and iodide analogues have been extensively described in the literature, arenesulfenyl fluorides remain essentially unstudied. These structures have been implicated as putative intermediates in established processes to access polyfluorinated sulfur species; however, definitive and direct evidence of their existence has not been obtained, nor has a systematic understanding of their reactivity. Here, we report the synthesis, isolation, and spectroscopic characterization of several arenesulfenyl fluorides, including structural analysis of 2,4-dinitrobenzenesulfenyl fluoride and 4-cyano-2-nitrobenzenesulfenyl fluoride by single-crystal X-ray diffraction. The functional group undergoes direct, efficient, and highly regioselective anti-addition to alkenes and alkynes, as well as insertion by carbenes. The resulting α- or β-fluoro thioether adducts can be readily transformed into useful fluorinated motifs, for example by modification of the sulfur groups (to sulfonamides or sulfonyl fluorides), by sulfur elimination (to generate formal C−H fluorination products), or by Julia–Kocienski olefination (to form vinyl fluorides). Thus, we establish that sulfenyl fluorides are unexpectedly accessible and stable compounds, which serve as versatile reagents for the production of fluorinated organic compounds.

Abstract Image

芳烃磺酰氟化物的合成及烯烃、炔和α-重氮羰基化合物的氟亚砜化反应
亚砜酰氟是硫的有机化合物,形式为氧化态+2,化学式为R-S-F。虽然氯化物、溴化物和碘化物的类似物在文献中已被广泛描述,但芳烃酰氟基本上尚未被研究。这些结构已被认为是获得多氟硫物种的既定过程中的假定中间体;然而,没有获得它们存在的明确和直接证据,也没有对它们的反应性有系统的了解。本文报道了几种呋喃磺酰氟化合物的合成、分离和光谱表征,包括用单晶x射线衍射分析了2,4-二硝基苯磺酰氟和4-氰基-2-硝基苯磺酰氟的结构。该官能团对烯烃和炔烃进行直接、高效和高度区域选择性的反加成反应,并被羰基插入。由此产生的α-或β-氟硫醚加合物可以很容易地转化为有用的氟化基序,例如,通过硫基团的改性(磺胺类或磺酰氟),通过硫消除(生成正式的碳氢氟化产物),或通过朱莉娅-科琴斯基烯烃(形成氟乙烯)。因此,我们确定,亚砜酰氟化合物是出乎意料的易于获取和稳定的化合物,可作为生产含氟有机化合物的通用试剂。
本文章由计算机程序翻译,如有差异,请以英文原文为准。
求助全文
约1分钟内获得全文 求助全文
来源期刊
CiteScore
26.60
自引率
6.60%
发文量
3549
审稿时长
1.5 months
期刊介绍: Angewandte Chemie, a journal of the German Chemical Society (GDCh), maintains a leading position among scholarly journals in general chemistry with an impressive Impact Factor of 16.6 (2022 Journal Citation Reports, Clarivate, 2023). Published weekly in a reader-friendly format, it features new articles almost every day. Established in 1887, Angewandte Chemie is a prominent chemistry journal, offering a dynamic blend of Review-type articles, Highlights, Communications, and Research Articles on a weekly basis, making it unique in the field.
×
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