Trimethyl-{2-[3-(tetrahydro-pyran-2-yloxy)-prop-1-ynyl]-phenylethynyl}-silane | 915237-88-6

• 分子结构分类: 有机化合物 - 苯类化合物 - 苯和取代衍生物
• 英文名称: Trimethyl-{2-[3-(tetrahydro-pyran-2-yloxy)-prop-1-ynyl]-phenylethynyl}-silane
• 英文别名: Trimethyl-[2-[2-[3-(oxan-2-yloxy)prop-1-ynyl]phenyl]ethynyl]silane
• CAS: 915237-88-6
• 化学式: C₁₉H₂₄O₂Si
• 分子量: 312.484
• InChiKey: JYFVSMCKCLFVRB-UHFFFAOYSA-N

物化性质

• 沸点：
  406.3±45.0 °C(Predicted)
• 密度：
  1.04±0.1 g/cm3(Temp: 20 °C; Press: 760 Torr)(Predicted)

计算性质

• 辛醇/水分配系数(LogP)：
  3.81
• 重原子数：
  22
• 可旋转键数：
  5
• 环数：
  2.0
• sp3杂化的碳原子比例：
  0.47
• 拓扑面积：
  18.5
• 氢给体数：
  0
• 氢受体数：
  2

反应信息

• 作为反应物：
  描述：

  Trimethyl-{2-[3-(tetrahydro-pyran-2-yloxy)-prop-1-ynyl]-phenylethynyl}-silane 在 乙基溴化镁 、 potassium carbonate 作用下， 以 四氢呋喃 、 甲醇 为溶剂， 反应 2.5h， 生成 1-Benzyloxy-4-{2-[3-(tetrahydro-pyran-2-yloxy)-prop-1-ynyl]-phenyl}-but-3-yn-2-ol
  参考文献：
  名称：

  Reaction of ene-bis(phosphinylallenes): [2+2] versus [4+2] cycloaddition

  摘要：

  Reaction of ene-bis(phosphinylallenes), derived from ene-bis(propargyl alcohols) and chlorodiphenylphosphine, was investigated. Benzene-bridged bis(phosphinylallenes) exclusively gave intramolecular [2+2] cycloadducts in the presence of dimethyl fumarate in sharp contrast to the reaction of benzene-bridged bis(sulfinylallenes), which gave the corresponding [4+2] cycloadducts. On the other hand, substituted ethylene- or five-membered heterocycle-bridged bis(phosphinylallenes) provided [4+2] cycloadducts. Reaction of benzene-bridged diallene bearing both a sulfinyl group and a phosphinyl group on the two allenyl groups was also described. (c) 2006 Elsevier Ltd. All rights reserved.

  DOI：

  10.1016/j.tet.2006.08.083
• 作为产物：
  描述：

  邻碘溴苯 在 bis-triphenylphosphine-palladium(II) chloride 、 copper(l) iodide 三乙胺 、 三苯基膦 作用下， 以 四氢呋喃 、 三乙胺 为溶剂， 反应 23.0h， 生成 Trimethyl-{2-[3-(tetrahydro-pyran-2-yloxy)-prop-1-ynyl]-phenylethynyl}-silane
  参考文献：
  名称：

  Reaction of ene-bis(phosphinylallenes): [2+2] versus [4+2] cycloaddition

  摘要：

  Reaction of ene-bis(phosphinylallenes), derived from ene-bis(propargyl alcohols) and chlorodiphenylphosphine, was investigated. Benzene-bridged bis(phosphinylallenes) exclusively gave intramolecular [2+2] cycloadducts in the presence of dimethyl fumarate in sharp contrast to the reaction of benzene-bridged bis(sulfinylallenes), which gave the corresponding [4+2] cycloadducts. On the other hand, substituted ethylene- or five-membered heterocycle-bridged bis(phosphinylallenes) provided [4+2] cycloadducts. Reaction of benzene-bridged diallene bearing both a sulfinyl group and a phosphinyl group on the two allenyl groups was also described. (c) 2006 Elsevier Ltd. All rights reserved.

  DOI：

  10.1016/j.tet.2006.08.083

文献信息

• Synthesis of Isoxazoline-Fused Bicyclic Enediynes via Intramolecular Nitrile Oxide-Alkene Cycloaddition
  作者：Amit Basak、Runa Pal

  DOI：10.1055/s-2008-1078244

  日期：2008.8

  The intramolecular nitrile oxide-alkene cycloaddition has been studied in an enediyne system. It has been shown to be an efficient method for one-step synthesis of isoxazoline-fused bicyclic enediynes. The thermal reactivity of these enediynes is similar to the isoxazolidine-fused counterparts, thus ruling out any significant effect by the bridgehead double bond.

  已在烯二炔系统中研究了分子内腈氧化物-烯烃环加成反应。它已被证明是一种一步合成异恶唑啉稠合双环烯二炔的有效方法。这些烯二炔的热反应性类似于异恶唑烷稠合的对应物，因此排除了桥头双键的任何显着影响。
• Conformationally Gated Fragmentations and Rearrangements Promoted by Interception of the Bergman Cyclization through Intramolecular H-Abstraction: A Possible Mechanism of Auto-Resistance to Natural Enediyne Antibiotics?
  作者：Abdulkader Baroudi、Justin Mauldin、Igor V. Alabugin

  DOI：10.1021/ja905100u

  日期：2010.1.27

  six-membered TS and transforms the p-benzyne into a new more stable radical. Depending on the substitution pattern and reaction conditions, this radical follows four alternative paths: (a) abstraction of an external hydrogen atom, (b) O-neophyl rearrangement which transposes O- and C-atoms of the substituent, (c) fragmentation of the O-C bond in the acetal ring, or (d) fragmentation with elimination of the appended

  在配备有缩醛环的烯二炔中，可以在伯格曼环化之后进行各种断裂和重排，模拟 esperamicine 和 calchiamicine 家族的天然烯二炔抗生素的碳水化合物部分。在所有这些过程的第一步中，分子内 H 原子提取通过六元 TS 有效拦截伯格曼环化的对苄产物，并将对苄转化为新的更稳定的自由基。根据取代模式和反应条件，该自由基遵循四种替代路径：(a) 外部氢原子的提取，(b) O-neophy 重排，其置换取代基的 O-和 C-原子，(c)缩醛环中的 OC 键，或 (d) 断裂并整体消除附加的缩醛部分。进行了不同浓度的外部 H 原子供体（1,4-环己二烯）的实验，以进一步了解分子间 H 抽象和碎片之间的竞争。gem-二甲基取代的烯二炔中的 Thorpe-Ingold 效应将碎裂效率提高到了即使大量过量的外部 H 原子供体也无法阻止的程度。这些过程使人们深入了解了 esperamicin A(1)
• Chemistry of enediynyl azides: activation through a novel pathway
  作者：Amit Basak、Sandip K. Roy、Sanket Das、Amrita B. Hazra、Subhash C. Ghosh、Shailendra Jha

  DOI：10.1039/b612114d

  日期：——

  The spontaneous activation of a nonaromatic enediynyl azide under ambient conditions has been demonstrated. The aromatic enediyne followed the expected cycloaddition with the alkene in the neighbouring arm to form a stable bridged bicyclic enediyne.

  研究证明了在环境条件下非芳香族烯二炔叠氮化物的自发活化。芳香族烯二炔与邻近臂中的烯发生了预期的环化反应，形成了稳定的桥式双环烯二炔。
• Reactivity of Bispropargyl Sulfones under Basic Conditions: Interplay Between Garratt-Braverman and Schmittel/Myers-Saito Cyclization Pathway
  作者：Raja Mukherjee、Sayantan Mondal、Amit Basak、Dibyendu Mallick、Eluvathingal D. Jemmis

  DOI：10.1002/asia.201100903

  日期：2012.5

  The preference for Garratt–Braverman (GB) over Myers–Saito (MS) and Schmittel (SCM) cyclizations has recently been demonstrated in sulfones capable of undergoing all three of the processes. As the GB cyclization is a self‐quenching process, there is a need to change the selectivity to the non‐self‐quenching MS or SCM pathway so as to enhance the DNA‐cleaving efficiency that operates through the radical‐mediated

  最近，在能够经历所有这三个过程的砜中，证明了Garratt-Braverman（GB）优于Myers-Saito（MS）和Schmittel（SCM）环化反应。由于GB环化是一个自我猝灭过程，因此需要改变对非自我猝灭MS或SCM途径的选择性，以提高通过自由基介导的过程进行DNA切割的效率。在这里，我们报告通过使用计算（M06-2X / 6-31 + G *）开发的基于构象约束的策略，将选择性从GB转换为MS / SCM途径，这也导致更大的DNA裂解活性。可以通过使用垫片来减轻约束，从而恢复对GB的偏爱。
• Design and synthesis of bisenediyne bissulfones and their reactivity under basic condition
  作者：Sanket Das、Amit Basak

  DOI：10.1016/j.bmcl.2009.03.094

  日期：2009.5

  A new class of bisenediyne bis sulfones has been synthesized. These molecules underwent cycloaromatization under basic conditions via isomerization to allene and were able to cleave ds-stranded plasmid DNA. (C) 2009 Published by Elsevier Ltd.