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
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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.
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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。
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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.
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