tris(pentafluorophenyl)silyl triflate | 844504-52-5

• 分子结构分类: 有机化合物 - 有机酸及其衍生物 - 有机磺酸及其衍生物
• 英文名称: tris(pentafluorophenyl)silyl triflate
• 英文别名: Methanesulfonic acid, trifluoro-, tris(pentafluorophenyl)silyl ester；tris(2,3,4,5,6-pentafluorophenyl)silyl trifluoromethanesulfonate
• CAS: 844504-52-5
• 化学式: C₁₉F₁₈O₃SSi
• 分子量: 678.33
• InChiKey: KUHHMSRXWWMNBV-UHFFFAOYSA-N

物化性质

• 沸点：
  400.5±45.0 °C(Predicted)
• 密度：
  1.83±0.1 g/cm3(Predicted)

计算性质

• 辛醇/水分配系数(LogP)：
  4.61
• 重原子数：
  42
• 可旋转键数：
  5
• 环数：
  3.0
• sp3杂化的碳原子比例：
  0.05
• 拓扑面积：
  51.8
• 氢给体数：
  0
• 氢受体数：
  21

反应信息

• 作为反应物：
  描述：

  tris(pentafluorophenyl)silyl triflate 在 吡啶 、 sodium acetate 作用下， 以 四氢呋喃 、 二氯甲烷 为溶剂， 反应 16.83h， 生成 (+/-)-N-methyl-N-(2-methyl-1-pentafluorophenylpropyl)-2-aminoethanol
  参考文献：
  名称：

  Synthesis of C₆F₅-Substituted Aminoethanols via Acetate Ion Mediated C₆F₅-Group Transfer Reaction

  摘要：

  本研究开发了一种合成 N-(五氟苯基甲基)氨基乙醇的新方法。该方法包括用环氧乙烷和 (C6F5)3SiOTf 制备的 2-三(五氟苯基)硅氧基乙基三酸酯对亚胺进行烷基化，从而得到 2-硅氧基乙基亚胺离子。它们经醋酸钠处理后，C-C 键形成的过程是 C6F5 基团从五配位硅酸盐中间体转移到亚胺中心的过程。

  DOI：

  10.1055/s-2006-926278
• 作为产物：
  描述：

  氯三(2,3,4,5,6-五氟苯基)硅烷 在 水 作用下， 以 二氯甲烷 、 二氯甲烷-D2 为溶剂， 反应 0.75h， 生成 tris(pentafluorophenyl)silyl triflate
  参考文献：
  名称：

  三(五氟苯基)硅烷醇(C6F5)3SiOH的合成、反应性和X射线晶体结构

  摘要：

  三(五氟苯基)硅烷醇(C 6 F 5 ) 3 SiOH通过非常规受控水解由相应的氯硅烷(C 6 F 5 ) 3 SiCl制备。报道了新硅烷醇与各种碱、三氟甲磺酸和一些铼羰基配合物的 X 射线结构和反应性。即使存在弱碱，Si-C 6 F 5键也很容易断裂，这种行为阻止了 (C 6 F 5 ) 3 SiO -阴离子的分离和 [Re(CO) 5 COSiR 3的合成] 衍生物。特别地，当(C 6 F 5 ) 3 SiOH与丁基锂和Re(CO) 5 OSO 2 CF 3反应时，观察到[Re(CO) 5 C 6 F 5 ]的形成。

  DOI：

  10.1016/j.ica.2021.120778

文献信息

• Activation of Carbon Dioxide by Silyl Triflate-Based Frustrated Lewis Pairs
  作者：Sarah A. Weicker、Douglas W. Stephan

  DOI：10.1002/chem.201501904

  日期：2015.9.7

  Silyl triflates of the form R4−nSi(OTf)n (n=1, 2; OTf=OSO3CF3) are shown to activate carbon dioxide when paired with bulky alkyl‐substituted Group 15 bases. Combinations of silyl triflates and 2,2,6,6‐tetramethylpiperidine react with CO2 to afford silyl carbamates via a frustrated Lewis pair‐type mechanism. With trialkylphosphines, the silyl triflates R3Si(OTf) reversibly bind CO2 affording [R′3P(CO2)SiR3][OTf]

  R 4- n Si（OTf）n（n = 1，2; OTf = OSO 3 CF 3）形式的甲硅烷基三氟甲磺酸酯与庞大的烷基取代的15组碱配对时，可以活化二氧化碳。甲硅烷基三氟甲磺酸酯和2,2,6,6-四甲基哌啶的混合物与CO 2反应，通过沮丧的Lewis对机制，生成氨基甲酸酯硅烷基酯。与三烷基膦，甲硅烷基三氟甲磺酸酯[R 3的Si（OTF）可逆地结合CO 2得到[R' 3 P（CO 2）的SIR 3 ] [光学传递函数]，而当PH 2的Si（OTF）2是使用一种或CO的两个分子2可以隔离。后者的bis-CO 2产品在低温下和过量的磷化氢很受青睐。
• Tris(pentafluorophenyl)silyl Triflate: Synthesis and Silylation of Carbonyl Compounds
  作者：Vitalij�V. Levin、Alexander�D. Dilman、Pavel�A. Belyakov、Alexander�A. Korlyukov、Marina�I. Struchkova、Vladimir�A. Tartakovsky

  DOI：10.1002/ejoc.200400552

  日期：2004.12

  Tris(pentafluorophenyl)silyl triflate (1) was prepared by protodesilylation of phenyl-, allyl-, and isopropenyloxytris(pentafluorophenyl)silyl derivatives and characterized by X-ray crystallography. This reagent was employed for the silylation of carbonyl compounds. Aldehydes and ketones afforded the corresponding silyl enol ethers in good yields, while silylation of esters and lactones was dependent

  三（五氟苯基）甲硅烷基三氟甲磺酸酯 (1) 是通过苯基-、烯丙基-和异丙烯氧基三（五氟苯基）甲硅烷基衍生物的原脱甲硅烷基化制备的，并通过 X 射线晶体学表征。该试剂用于羰基化合物的甲硅烷基化。醛和酮以良好的产率提供相应的甲硅烷基烯醇醚，而酯和内酯的甲硅烷基化取决于反应条件和底物。提出了一种解释观察到的现象的机制。还介绍了 1 和三氟甲磺酸三甲基甲硅烷基酯的相对反应性研究。(© Wiley-VCH Verlag GmbH & Co. KGaA, 69451 Weinheim, Germany, 2004)
• On the interaction of silyl triflates with enamines: iminium ion formation versus silylation
  作者：Vitalij V. Levin、Alexander D. Dilman、Pavel A. Belyakov、Alexander A. Korlyukov、Marina I. Struchkova、Vladimir A. Tartakovsky

  DOI：10.1016/j.tetlet.2005.03.144

  日期：2005.5

  The interaction of Me3SiOTf and (C6F5)3SiOTf with enamines generating α-silyl-substituted iminium ions is investigated. A trimethylsilyl iminium cation is formed as a long-lived species observable by NMR spectroscopy, whilst the tris(pentafluorophenyl)silyl analogue is very labile and prone to the loss of a proton. On the basis of the latter phenomenon, a method for the synthesis of β-silyl enamines

  研究了Me 3 SiOTf和（C 6 F 5）3 SiOTf与生成α-甲硅烷基取代的亚胺离子的烯胺的相互作用。可以通过NMR光谱观察到长寿命的物种是三甲基甲硅烷基亚胺阳离子，而三（五氟苯基）甲硅烷基类似物非常不稳定，容易发生质子损失。基于后一种现象，提出了一种合成β-甲硅烷基烯胺的方法。
• Synthesis and structures of tris(pentafluorophenyl)silylamines
  作者：V. V. Levin、A. D. Dilman、A. A. Korlyukov、P. A. Belyakov、M. I. Struchkova、M. Yu. Antipin、V. A. Tartakovsky

  DOI：10.1007/s11172-007-0213-y

  日期：2007.7

  Tris(pentafluorophenyl)silylamines were synthesized by silylation of amines and imines with (C6F5)3SiCl or (C6F5)3SiOTf in the presence of triethylamine. The crystal structures of the (C6F5)3SiN(H)CH2Ph and (C6F5)3SiN(CH=CMe2)CH2Ph compounds were studied by X-ray diffraction. The crystal packings were analyzed by quantum chemical calculations in terms of the density functional theory (PBE exchange-correlation functional).

  在三乙胺存在下，用 (C6F5)3SiCl 或 (C6F5)3SiOTf 对胺和亚胺进行硅烷化，合成了三(五氟苯基)硅胺。通过 X 射线衍射研究了 (C6F5)3SiN(H)CH2Ph 和 (C6F5)3SiN(CH=CMe2)CH2Ph 化合物的晶体结构。根据密度泛函理论（PBE 交换相关函数），通过量子化学计算分析了晶体堆积。
• Complexation of tris(pentafluorophenyl)silanes with neutral Lewis bases
  作者：Alexander D. Dilman、Vitalij V. Levin、Alexander A. Korlyukov、Pavel A. Belyakov、Marina I. Struchkova、Mikhail Yu. Antipin、Vladimir A. Tartakovsky

  DOI：10.1016/j.jorganchem.2007.12.022

  日期：2008.3

  A detailed analysis of monodentate and bidentate complexation of tris(pentafluorophenyl) silyl (TPFS) derivatives with neutral Lewis bases was performed. The NMR spectroscopy and X-ray diffraction analysis (11 structures) were the key methods to characterize tetraor pentacoordinate silicon compounds, whereas the peculiarities of crystal packing were analyzed by means of DFT calculations. The interaction of TPFS-X (X = F, Cl, OTf) with strong Lewis bases (HMPA, N-methylpyrrolidinone) may afford three different species: neutral pentacoordinate TPFS(X)-L, cationic tetracoordinate TPFS-L+ X-, and cationic pentacoordinate TPFS-(L)(2)X-+(-), representatives of each type were characterized by X-ray diffraction. A variety of complexes with bidentate complexation, featuring the trigonal bipyramidal geometry with apical C6F5-group was prepared and structurally characterized. The extent of Si-C-apical bond elongation depends on the donating ability of the coordinating ligand, with the longest Si-C bond of 1.981(1) angstrom observed for six-membered complex of TPFS-ether of N-(2-hydroxybenzoyl) pyrrolidine. (C) 2007 Elsevier B.V. All rights reserved.