Direct synthesis of N-perfluoro-tert-butyl secondary amines from N-trifluoromethyl secondary amines

IF 7.6 1区 化学 Q1 CHEMISTRY, MULTIDISCIPLINARY Chemical Science Pub Date : 2024-11-06 DOI:10.1039/d4sc06335j
leibing Wang, Zhongyu Feng, Zhen Luo, Zihao Guo, Jieping Wang, WenBin Yi
{"title":"Direct synthesis of N-perfluoro-tert-butyl secondary amines from N-trifluoromethyl secondary amines","authors":"leibing Wang, Zhongyu Feng, Zhen Luo, Zihao Guo, Jieping Wang, WenBin Yi","doi":"10.1039/d4sc06335j","DOIUrl":null,"url":null,"abstract":"N-Perfluoro-tert-butyl (N-PFtB) secondary amines, harboring a unique 19F-reporting moiety linked directly to nitrogen, are highly attractive due to their diverse potential applications. However, their mild and facile synthesis remains a significant challenge. Herein, we present a safe and efficient strategy for the direct synthesis of N-perfluoro-tert-butyl secondary amines from readily available N-trifluoromethyl secondary amines. Experiments and theoretical calculations demonstrate that this novel protocol encompasses three main processes: the elimination of hydrogen fluoride from the N-trifluoromethyl precursor, consecutive addition-elimination conversion of difluoromethyl imine (R-N=CF2) to hexafluoropropyl imine (R-N=C(CF3)2), and final addition of R-N=C(CF3)2 with the in situ generated fluoroform (HCF3). Key advantages of this reaction include the utilization of a single trifluoromethyl source and the N-trifluoromethyl starting material itself as the hydrogen source. Notably, the elimination of hydrogen fluoride, facilitated by CsF, is critical for the success of this approach. This method is compatible with a broad range of functional groups, including heterocyclic compounds. 19F MRI experiments suggest promising prospects for PFtB-labeled secondary amines as 19F MRI contrast agents.","PeriodicalId":9909,"journal":{"name":"Chemical Science","volume":"144 1","pages":""},"PeriodicalIF":7.6000,"publicationDate":"2024-11-06","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":"0","resultStr":null,"platform":"Semanticscholar","paperid":null,"PeriodicalName":"Chemical Science","FirstCategoryId":"92","ListUrlMain":"https://doi.org/10.1039/d4sc06335j","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

N-Perfluoro-tert-butyl (N-PFtB) secondary amines, harboring a unique 19F-reporting moiety linked directly to nitrogen, are highly attractive due to their diverse potential applications. However, their mild and facile synthesis remains a significant challenge. Herein, we present a safe and efficient strategy for the direct synthesis of N-perfluoro-tert-butyl secondary amines from readily available N-trifluoromethyl secondary amines. Experiments and theoretical calculations demonstrate that this novel protocol encompasses three main processes: the elimination of hydrogen fluoride from the N-trifluoromethyl precursor, consecutive addition-elimination conversion of difluoromethyl imine (R-N=CF2) to hexafluoropropyl imine (R-N=C(CF3)2), and final addition of R-N=C(CF3)2 with the in situ generated fluoroform (HCF3). Key advantages of this reaction include the utilization of a single trifluoromethyl source and the N-trifluoromethyl starting material itself as the hydrogen source. Notably, the elimination of hydrogen fluoride, facilitated by CsF, is critical for the success of this approach. This method is compatible with a broad range of functional groups, including heterocyclic compounds. 19F MRI experiments suggest promising prospects for PFtB-labeled secondary amines as 19F MRI contrast agents.
查看原文
分享 分享
微信好友 朋友圈 QQ好友 复制链接
本刊更多论文
从 N-三氟甲基仲胺直接合成 N-全氟叔丁基仲胺
N- 全氟叔丁基(N-PFtB)仲胺含有一个直接与氮相连的独特的 19F 报告分子,因其具有多种潜在应用而极具吸引力。然而,如何温和、简便地合成它们仍然是一个重大挑战。在此,我们提出了一种安全、高效的策略,利用现成的 N-三氟甲基仲胺直接合成 N-全氟叔丁基仲胺。实验和理论计算表明,这种新型方案包括三个主要过程:从 N-三氟甲基前体中消除氟化氢、二氟甲基亚胺(R-N=CF2)连续加成-消除转化为六氟丙基亚胺(R-N=C(CF3)2),以及 R-N=C(CF3)2 与原位生成的氟仿(HCF3)的最终加成。该反应的主要优点包括利用单一的三氟甲基源和 N-三氟甲基起始原料本身作为氢源。值得注意的是,通过 CsF 消除氟化氢对这种方法的成功至关重要。这种方法与包括杂环化合物在内的多种官能团兼容。19F MRI 实验表明,PFtB 标记的仲胺作为 19F MRI 造影剂前景广阔。
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 去求助
来源期刊
Chemical Science
Chemical Science CHEMISTRY, MULTIDISCIPLINARY-
CiteScore
14.40
自引率
4.80%
发文量
1352
审稿时长
2.1 months
期刊介绍: Chemical Science is a journal that encompasses various disciplines within the chemical sciences. Its scope includes publishing ground-breaking research with significant implications for its respective field, as well as appealing to a wider audience in related areas. To be considered for publication, articles must showcase innovative and original advances in their field of study and be presented in a manner that is understandable to scientists from diverse backgrounds. However, the journal generally does not publish highly specialized research.
期刊最新文献
Adding multiple electrons to helicenes: how they respond? Dynamic selection in metallo-organic cube CdⅡ8L4 conformations induced by perfluorooctanoate encapsulation Assessment of Fine-Tuned Large Language Models for Real-World Chemistry and Material Science Applications Ag(I) emitters with ultrafast spin-flip dynamics for high-efficiency electroluminescence Cooperative Photoredox and N-Heterocyclic Carbene-Catalyzed Formal C-H Acylation of Cyclopropanes via Deconstruction-Reconstruction Strategy
×
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
现在去查看 取消
×
提示
确定
0
微信
客服QQ
Book学术公众号 扫码关注我们
反馈
×
意见反馈
请填写您的意见或建议
请填写您的手机或邮箱
已复制链接
已复制链接
快去分享给好友吧!
我知道了
×
扫码分享
扫码分享
Book学术官方微信
Book学术文献互助
Book学术文献互助群
群 号:481959085
Book学术
文献互助 智能选刊 最新文献 互助须知 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 Book学术 All rights reserved.
ghs 京公网安备 11010802042870号 京ICP备2023020795号-1