trimethylsilyl perchlorate | 18204-79-0

• 分子结构分类: 有机化合物 - 有机氧化合物 - 有机含氧阴离子化合物
• 英文名称: trimethylsilyl perchlorate
• 英文别名: trimethylsilyl*ClO4；perchloric acid trimethylsilanyl ester；Perchlorsaeure-trimethylsilylester；Trimethyl-perchloryloxy-silan；Trimethylsilylperchlorat
• CAS: 18204-79-0
• 化学式: C₃H₉ClO₄Si
• 分子量: 172.641
• InChiKey: WJTPULFEHRBUCP-UHFFFAOYSA-N

物化性质

• 沸点：
  35-38 °C(Press: 14 Torr)

计算性质

• 辛醇/水分配系数(LogP)：
  -2.26
• 重原子数：
  9
• 可旋转键数：
  1
• 环数：
  0.0
• sp3杂化的碳原子比例：
  1.0
• 拓扑面积：
  60.4
• 氢给体数：
  0
• 氢受体数：
  4

反应信息

• 作为反应物：
  描述：

  trimethylsilyl perchlorate 、 三甲基硅咪唑 以 正己烷 、 甲苯 为溶剂， 反应 0.17h， 生成 bistrimethylsilylimidazolium perchlorate
  参考文献：
  名称：

  Bassindale, Alan R.; Stout, Tim, Journal of the Chemical Society. Perkin transactions II, 1986, p. 221 - 226

  摘要：

  DOI：
• 作为产物：
  描述：

  三甲基氯硅烷 在 silver perchlorate 作用下， 以 乙醚 为溶剂， 反应 0.17h， 生成 trimethylsilyl perchlorate
  参考文献：
  名称：

  用糖基N-三氯乙酰氨基甲酸酯改善的催化和立体选择性糖基化：应用于各种1-羟基糖。

  摘要：

  在存在糖基受体和5A分子筛的情况下，通过用催化量的路易斯酸活化N-三氯乙酰氨基甲酸糖基，可以实现有效的催化和立体选择性糖基化。通过与三氯乙酰基异氰酸酯反应，然后用催化量的活化剂活化，选择性地实现了1-羟基碳水化合物的催化一锅脱水糖基化反应。

  DOI：

  10.1016/j.carres.2010.01.011
• 作为试剂：
  描述：

  胆固醇 、 2,3,4,6-tetra-O-benzyl-α-D-glucopyranosyl N-trichloroacetylcarbamate 在 trimethylsilyl perchlorate 作用下， 以 乙醚 为溶剂， 反应 4.0h， 以93%的产率得到cholesteryl 2,3,4,6-tetra-O-benzyl-D-glucopyranoside
  参考文献：
  名称：

  Catalytic and stereoselective glycosylation with glycosyl N-trichloroacetylcarbamate

  摘要：

  Catalytic and stereoselective glycosylation efficiently proceeded by activating a glycosyl N-trichloroacetylcarbamate with a catalytic amount of Lewis acids in the presence of a glycosyl acceptor and molecular sieves 5 angstrom. Catalytic and one-pot dehydrative glycosylation of a 1-hydroxy carbohydrate was also performed stereoselectively by the reaction with trichloroacetyl isocyanate followed by activation with a catalytic amount of activators. (c) 2005 Elsevier Ltd. All rights reserved.

  DOI：

  10.1016/j.tetlet.2005.11.027

文献信息

• Transmission of Point Chirality to Axial Chirality for Strong Circular Dichroism in Triarylmethylium-o,o-dimers
  作者：Takanori Suzuki、Yusuke Ishigaki、Tomohiro Iwai、Yuki Hayashi、Aiichiro Nagaki、Ryo Katoono、Kenshu Fujiwara、Jun-ichi Yoshida

  DOI：10.1055/s-0037-1610190

  日期：2018.10

  auxiliaries on the aryl groups induce a preference in the axial chirality of the central biphenyl unit. Strong circular dichroism is attained through exciton coupling, which can be used for additional spectral output in their electrochromic behavior. Diastereoselectivity based on π–π stacking exhibits unique solvent effects, thus endowing multifunctional response properties.

  三芳甲基鎓-o,o-二聚体采用扭曲的几何结构，使两个二芳甲基鎓以滑动方式堆叠。因此，芳基上的手性助剂导致了中心联苯单元的轴向手性的偏好。通过激子耦合获得强圆二色性，可用于在其电致变色行为中提供额外的光谱输出。基于 π-π 堆积的非对映选择性表现出独特的溶剂效应，从而赋予多功能响应特性。
• Multi-Input/Multi-Output Molecular Response System Based on the Dynamic Redox Behavior of 3,3,4,4-Tetraaryldihydro[5]helicene Derivatives: Reversible Formation/Destruction of Chiral Fluorophore and Modulation of Chiroptical Properties by Solvent Polarity
  作者：Takanori Suzuki、Yusuke Ishigaki、Tomohiro Iwai、Hidetoshi Kawai、Kenshu Fujiwara、Hiroshi Ikeda、Yusuke Kano、Kazuhiko Mizuno

  DOI：10.1002/chem.200900968

  日期：2009.9.21

  3,3,4,4‐Tetaaryldihydro[5]helicenes (1) and 1,1′‐binaphthyl‐2,2′‐diylbis(diarylcarbenium)s (22+) can be reversibly interconverted upon electron transfer, which is accompanied by a vivid color change (electrochromism) as well as by the formation/cleavage of a CC bond (“dynamic redox behavior”). Because only the neutral donor 1 exhibits strong fluorescence, electrochemical input can further modify the

  3,3,4,4-四芳基二氢[5]螺旋烯（1）和1,1'-联萘-2-2,2'-二基双（二芳基碳鎓）（2 2+）可以在电子转移时可逆地相互转化，这伴随着通过生动的颜色变化（电致变色）以及CC键的形成/断裂（“动态氧化还原行为”）。因为仅中性供体1显示强荧光，所以电化学输入可进一步改变该对的荧光性质。由于1的螺旋度和2 2+的轴向手性的构型稳定性，光学纯净材料的氧化还原反应会立体定向进行，从而引起手性​​变化，例如圆二色性（CD）作为附加输出。指示剂2 2+的CD光谱显示出溶剂依赖性（手性溶剂致变色），伴随着基于两个阳离子发色团π-π相互作用的溶色行为以及Lewis碱性溶剂与Lewis酸性三芳基碳鎓的配位相互作用部分。因此，本系统具有用于修改多个输出信号的多输入功能。
• Comparison between Electron Transfer and Nucleophilic Reactivities of Ketene Silyl Acetals with Cationic Electrophiles
  作者：Shunichi Fukuzumi、Kei Ohkubo、Junzo Otera

  DOI：10.1021/jo005733g

  日期：2001.2.1

  d ketene silyl acetal (1: (Me2C=C(OMe)OSiMe3) with trityl cation salt (Ph3C+ClO4-) takes place between 1 and the carbon of para-positon of phenyl group of Ph3C+, whereas a much less sterically hindered ketene silyl acetal (3: H2C=C(OEt)OSiEt3) reacts with Ph3C+ at the central carbon of Ph3C+. The kinetic comparison indicates that the nucleophilic reactivities of ketene silyl acetals are well correlated

  研究了酮甲硅烷基缩醛与一系列对甲氧基取代的三苯甲基阳离子反应的产物和动力学，并将其与由10,10'-二甲基-9,9进行的外球电子转移反应进行了比较。 '，10，10'-四氢-9,9'-二cr啶[（AcrH）2]形成相同系列的三苯甲基阳离子以及其他电子受体。β，β-二甲基取代的烯酮甲硅烷基缩醛（1：（Me2C = C（OMe）OSiMe3）与三苯甲基阳离子盐（Ph3C + ClO4-）的反应中的CC键形成在1和对位碳之间Ph3C +的苯基正位置，而空间位阻少得多的乙烯酮甲硅烷基乙缩醛（3：H2C = C（OEt）OSiEt3）在Ph3C +的中心碳上与Ph3C +反应。
• Fukuzumi, Shunichi; Kitano, Toshiaki; Mochida, Kunio, Chemistry Letters, 1989, p. 2177 - 2180
  作者：Fukuzumi, Shunichi、Kitano, Toshiaki、Mochida, Kunio

  DOI：——

  日期：——
• Homogeneous Catalysis. Mechanisms of the Catalytic Mukaiyama Aldol and Sakurai Allylation Reactions
  作者：T. Keith Hollis、B. Bosnich

  DOI：10.1021/ja00121a015

  日期：1995.4

  The mechanisms of a number of Mukaiyama aldol and Sakurai allylation reactions catalyzed by the Lewis acids [Ti(Cp)(2)(OTf)(2)], Ph(3)COTf, and Ph(3)CClO(4) have been investigated. It is found that hydrolysis of the Lewis acid by trace amounts of water in the solvent can lead to the formation of acid. The acid then reacts with the silyl enol ether or allylic silane to generate Me(3)SiOTf or Me(3)SiClO(4), both of which are powerful catalysts for these reactions. Dehydration of the solvent or addition of a hindered base to quench the acid does not necessarily prevent the formation of these silyl catalysts. In the case of the [Ti(Cp)(2)(OTf)(2)] Lewis acid, Me(3)SiOTf is generated as a consequence of the mechanism, and it is shown that all of the catalysis proceeds by the Me(3)SiOTf species and that [Ti(Cp)(2)(OTf)(2)] acts only as an initiator for the production of Me(3)SiOTf. For the case of the presumed Ph(3)COTf catalyst, the Mukaiyama aldol reaction proceeds exclusively by the Me(3)SiOTf catalyst and Ph(3)COTf is neither an initiator nor a catalyst. It generates Me(3)SiOTf by hydrolysis. It is shown that the rate and stereoselectivity of Me(3)SiOTf catalysis depend on the concentration of triflate ions. The rate slows and the selectivity switches with an increase in triflate concentration. The rate of Sakurai catalysis of allylsilane with an acetal using Ph(3)CClO(4) can be quantitatively accounted for by invoking only Me(3)SiClO(4) catalysis. The Me(3)SiClO(4) can be generated by hydrolysis, but when this is suppressed, Me(3)SiClO(4) can be formed by allylation of Ph(3)CClO(4). It is suggested that many of the reported catalysts may only be agents for the production of the real catalysts, namely, Me(3)SiX species. The characteristics of Lewis acids which may obviate the intrusion of Me(3)SiX catalysis are outlined.