三苯甲基三氟甲烷磺酸酯 | 64821-69-8

• 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
• 中文名称: 三苯甲基三氟甲烷磺酸酯
• 英文名称: trityl triflate
• 英文别名: trityl trifluoromethanesulfonate；tritylium triflate；diphenylmethylbenzene;trifluoromethanesulfonate
• CAS: 64821-69-8
• 化学式: CF₃O₃S*C₁₉H₁₅
• 分子量: 392.399
• InChiKey: IEZOKZHBOQDYGI-UHFFFAOYSA-M

物化性质

• 熔点：
  112-117 °C

计算性质

• 辛醇/水分配系数(LogP)：
  4.76
• 重原子数：
  27
• 可旋转键数：
  3
• 环数：
  3.0
• sp3杂化的碳原子比例：
  0.05
• 拓扑面积：
  65.6
• 氢给体数：
  0
• 氢受体数：
  6

安全信息

• 危险等级：
  8
• 危险品标志：
  C
• 安全说明：
  S26,S36/37/39,S45
• 危险类别码：
  R34
• 海关编码：
  2904909090
• 包装等级：
  III
• 危险品运输编号：
  UN 3261 8/PG 2

反应信息

• 作为反应物：
  描述：

  三苯甲基三氟甲烷磺酸酯 以 二氯甲烷 为溶剂， 反应 24.08h， 生成 trifluoromethanesulfonic acid compound with (4-benzhydrylphenyl)di-tert-butylphosphane (1:1)
  参考文献：
  名称：

  Frustrated Lewis pair-mediated C–O or C–H bond activation of ethers

  摘要：

  FLP介导的醚类转化的协议已呈现。

  DOI：

  10.1039/c4cc01922a
• 作为产物：
  描述：

  三苯基甲醇 、 三氟甲磺酸 生成 三苯甲基三氟甲烷磺酸酯
  参考文献：
  名称：

  Charge Delocalization and Enhanced Acidity in Tricationic Superelectrophiles

  摘要：

  This Article presents the results from studies related to the chemistry of tricationic superelectrophiles. A series of triaryl methanols were ionized in Bronsted superacids, and the corresponding tricationic intermediates were formed. The trications are found to participate in two types of reactions; both are characteristic of highly charged organic cations. One set of reactions occurs through charge migration. A second set of reactions occurs through deprotonation of an unusually acidic site on the tricationic species. One of the tricationic intermediates has been directly observed by low temperature NMR spectroscopy. These highly charged ions and their reactions have also been studied using density functional theory calculations. As a result of charge migration, electron density at a carbocation site is found to increase with progression from monocationic to pentacationic structures.

  DOI：

  10.1021/ja2046364
• 作为试剂：
  描述：

  3,4,6-tri-O-acetyl-1,2-O-<1-(cyano)ethylidene>-α-D-galactopyranose 、 Methyl 2,4,6-Tri-O-acetyl-3-O-trityl-β-D-galactopyranoside 在 三苯甲基三氟甲烷磺酸酯 作用下， 以 二氯甲烷 为溶剂， 反应 17.0h， 生成 Gal2Ac3Ac4Ac6Ac(b1-3)b-Gal1Me2Ac4Ac6Ac 、 [(2R,3S,4S,5R,6R)-3,5-diacetyloxy-6-methoxy-4-[(2R,3R,4S,5S,6R)-3,4,5-triacetyloxy-6-(acetyloxymethyl)oxan-2-yl]oxyoxan-2-yl]methyl acetate
  参考文献：
  名称：

  Glycosylation by sugar 1,2-O-(1-cyanobenzylidene) derivatives: influence of glycosyl-donor structure and promoter

  摘要：

  3,4,6-Tri-O-acetyl-1,2-O-(1-cyanobenzylidene)-alpha-D-galactopyranoses with differently substituted aromatic nuclei have been synthesised and used as glycosyl donors in reactions with the acceptors methyl 2,3,4-tri-O-acetyl-6-O-trityl-beta-D-galactopyranoside (11) and methyl 2,4,6-tri-O-acetyl-3-O-trityl-beta-D-galactopyranoside (12). The glycosylation of 11 gave only beta products. The efficiency and stereoselectivity of the glycosylations of 12 depend on the nature of the substituent in the aromatic ring. The stereoselectivity for the formation of 1,2-trans-glycosidic bonds was the highest with the p-methoxy-benzylidene derivative with triphenylmethylium triflate as the promoter.

  DOI：

  10.1016/0008-6215(93)80006-z

文献信息

• The Oxidative Michael Reaction. A Highly Diastereoselective Synthesis of 5-Oxocarboxylic Acid Derivatives
  作者：Yukihiko Hashimoto、Teruaki Mukaiyama

  DOI：10.1246/cl.1986.1623

  日期：1986.9.5

  Methyldiphenylsilyl enol ethers react with an allylic cation stabilized by two sulfur atoms in a highly anti-selective manner to afford 5-oxocarboxylic acid derivatives.

  甲基二苯基硅基烯醇醚与由两个硫原子稳定的烯丙基阳离子以高度反选择性方式反应，生成5-氧代羧酸衍生物。
• Silicon Tetrakis(trifluoromethanesulfonate): A Simple Neutral Silane Acting as a Soft and Hard Lewis Superacid
  作者：André Hermannsdorfer、Matthias Driess

  DOI：10.1002/anie.202103414

  日期：2021.6.7

  leads to [L2Si(OTf)4] complexes (L=isocyanide, thioether and carbonyl compounds) with retention of all Si−OTf bonds. In contrast, it can cleave C−X bonds (X=F, Cl) of hard organic Lewis bases with a high tendency to form SiX4 (X=F, Cl) after halide/triflate exchange. Most notable, Si(OTf)4 allows a gentle oxydefluorination of mono- and bis(trifluoromethyl)benzenes, resulting in the formation of the corresponding

  据报道，原始硅四（三氟甲磺酸）Si(OTf) 4的简单合成和分离是第一种适用于软和硬路易斯碱的中性硅基路易斯超强酸。其 OTf 基团具有双重功能：它们是优异的离去基团，并调节对软路易斯碱和硬路易斯碱的反应程度。暴露于软路易斯供体时，Si(OTf) 4产生[L 2 Si(OTf) 4 ]配合物（L=异氰化物、硫醚和羰基化合物），并保留所有Si−OTf键。相反，它可以裂解硬有机路易斯碱的CX键（X = F，Cl），并且在卤化物/三氟甲磺酸酯交换后很容易形成SiX 4 （X = F，Cl）。最值得注意的是，Si(OTf) 4允许单（三氟甲基）苯和双（三氟甲基）苯发生温和的氧化脱氟反应，从而形成相应的苯甲酰鎓物种，并通过弱配位的[Si(OTf) 6 ]二价阴离子进行稳定。
• Triflyloxy-substituted carboranes as useful weakly coordinating anions
  作者：Loren P. Press、Billy J. McCulloch、Weixing Gu、Chun-Hsing Chen、Bruce M. Foxman、Oleg V. Ozerov

  DOI：10.1039/c5cc05047b

  日期：——

  New carborane anions carrying one or three triflyloxy substituents are described.

  描述了带有一个或三个三氟甲磺氧基取代基的新卡博烷阴离子。
• Silylene-assisted hydride transfer to CO₂ and CS₂ at a [P₂Si]Ru pincer-type complex
  作者：Matthew T. Whited、Jia Zhang、Senjie Ma、Binh D. Nguyen、Daron E. Janzen

  DOI：10.1039/c7dt03659k

  日期：——

  The synthesis and characterization of base-stabilized and base-free pincer-type bis(phosphine)/silylene [P2Si]Ru complexes are reported. The base-free complex readily reduces CO2 and CS2 via silylene-assisted hydride transfer, affording structurally distinct products with silicon-to-ruthenium formate and dithioformate bridges.

  报道了碱稳定的无碱钳型双（膦）/亚甲硅烷基[P 2 Si] Ru配合物的合成和表征。不含碱的配合物可通过甲硅烷基辅助的氢化物转移轻松还原CO 2和CS 2 ，从而提供结构上截然不同的产物，包括甲硅酸钌和二硫代甲酸酯桥。
• Zinc-Mediated Transmetalation as a Route to Anionic <i>N</i>-Heterocyclic Olefin Complexes in the p-Block
  作者：Ian C. Watson、Michael J. Ferguson、Eric Rivard

  DOI：10.1021/acs.inorgchem.1c02961

  日期：2021.12.6

  tunability and strong σ- and π-electron donating abilities. In this study, the new two-coordinate zinc complex (MeIPrCH)2Zn (MeIPrCH = [(MeCNDipp)2C═CH]−, Dipp = 2,6-diisopropylphenyl) is shown to participate in a broad range of metathesis reactions with main group element-based halides and hydrides. In the case of the group 14 halides, Cl2E·dioxane (E = Ge and Sn), transmetalation occurs to form dinuclear

  阴离子N-杂环烯烃 (aNHO) 因其空间可调性和强大的 σ- 和 π- 给电子能力，非常适合用于稳定低配位无机配合物。在这项研究中，新的双配位锌络合物 ( Me IPrCH) 2 Zn ( Me IPrCH = [(MeCNDipp) 2 C= CH] - , Dipp = 2,6-二异丙基苯基) 显示参与广泛的复分解与基于主族元素的卤化物和氢化物发生反应。在第 14 族卤化物 Cl 2 E·二恶烷（E = Ge 和 Sn）的情况下，发生金属转移形成双核推进器形阳离子 [( Me IPrCHE) 2 (μ-Cl)] +，而aNHO封端的膦配体我IPrCH-PPH 2时（获得我IPrCH）2的Zn与ClPPh组合2。最后，消除ZnH 2驱动 ( Me IPrCH) 2 Zn 与氢硼烷和氢铝烷之间的金属转移，导致路易斯酸性 aNHO 负载的 -硼基和 -铝烷产物。