Maibom Kristina A M, Breitenstein Christoph, Lorenzen Sabine, Knuplez Tanja, Schneider Leon N, Bejaoui Younes K J, Gierling Johannes, Radacki Krzysztof, Braunschweig Holger, Deutsch Carl, Shan Min, Fuchß Thomas, Schulte Michael, Ignat'ev Nikolai V, Finze Maik
Institute of Inorganic Chemistry, Institute for Sustainable Chemistry & Catalysis with Boron (ICB), University of Würzburg, Am Hubland, 97074, Würzburg, Germany.
Institute of Inorganic Chemistry and Structural Chemistry II, University of Düsseldorf, Universitätsstr. 1, 40225, Düsseldorf, Germany.
Chemistry. 2025 Jul 11;31(39):e202501550. doi: 10.1002/chem.202501550. Epub 2025 Jun 16.
N,N-Bis(trifluoromethyl)aminoacetonitrile (CF)NCHCN (1) that is accessible via a simple single-step protocol is established as a building block for the introduction of the (CF)N group. The two reaction sites of 1, the methylene unit and the nitrile (cyano) group, provide access to different organic substance classes. This includes alkenes via Knoevenagel condensations, and N-heterocycles and acid derivatives obtained by addition reactions to the nitrile unit. These new (CF)N derivatives are potential building blocks containing the bis(trifluoromethyl)amino group. Deprotonation of 1 at the methylene group highlights the electron-withdrawing nature of the (CF)N group. The {(CF)NCHCN} anion (1) is characterized by NMR spectroscopy and its reaction with [PhPAuCl] results in [PhPAuCH{N(CF)}(CN)] (Au1) and [(PhPAu)C{N(CF)}(CN)] (Au1). Crystal structure analysis of (CF)NCHCN (1), Au1, and almost all alkenes, N-heterocycles, and acid derivatives with a (CF)N group combined with spectroscopic data and results from DFT calculations provide insight into properties of the highly fluorinated (CF)N substituent. Especially the ability of the amino nitrogen atom to participate in weak hydrogen bonding, albeit its low basicity, is of relevance.
通过简单的一步法可获得的N,N-双（三氟甲基）氨基乙腈（CF）NCHCN（1）被确立为引入（CF）N基团的一个结构单元。1的两个反应位点，即亚甲基单元和腈（氰基）基团，可通向不同的有机物质类别。这包括通过克诺文格尔缩合反应得到的烯烃，以及通过向腈单元进行加成反应获得的N-杂环和酸衍生物。这些新的（CF）N衍生物是含有双（三氟甲基）氨基的潜在结构单元。1在亚甲基处的去质子化突出了（CF）N基团的吸电子性质。{（CF）NCHCN}阴离子（1）通过核磁共振光谱进行了表征，并且它与[PhPAuCl]的反应生成了[PhPAuCH{N（CF）}（CN）]（Au1）和[（PhPAu）C{N（CF）}（CN）]（Au1）。（CF）NCHCN（1）、Au1以及几乎所有带有（CF）N基团的烯烃、N-杂环和酸衍生物的晶体结构分析，结合光谱数据和密度泛函理论计算结果，为深入了解高度氟化的（CF）N取代基的性质提供了依据。特别是氨基氮原子尽管碱性较低但仍能参与弱氢键形成的能力具有重要意义。
