3-methyl-1,5-bis(trimethylsilyl)penta-1,4-diyn-3-ol | 13888-90-9

• 分子结构分类: 有机化合物 - 有机氧化合物
• 英文名称: 3-methyl-1,5-bis(trimethylsilyl)penta-1,4-diyn-3-ol
• CAS: 13888-90-9
• 化学式: C₁₂H₂₂OSi₂
• 分子量: 238.477
• InChiKey: FXGIMLVQPBBHHT-UHFFFAOYSA-N

物化性质

• 熔点：
  35 °C
• 沸点：
  105-106 °C(Press: 4 Torr)
• 密度：
  0.909±0.06 g/cm3(Predicted)

计算性质

• 辛醇/水分配系数(LogP)：
  2.5
• 重原子数：
  15
• 可旋转键数：
  4
• 环数：
  0.0
• sp3杂化的碳原子比例：
  0.67
• 拓扑面积：
  20.2
• 氢给体数：
  1
• 氢受体数：
  1

反应信息

• 作为反应物：
  描述：

  3-methyl-1,5-bis(trimethylsilyl)penta-1,4-diyn-3-ol 在 甲醇 、 potassium carbonate 作用下， 以60%的产率得到3-methyl-1,4-pentadiyne-3-ol
  参考文献：
  名称：

  迈向Jerangolids的全合成-药理学亚基的高级中间体的合成

  摘要：

  在这里，我们提出了一种以跳过的二炔为主要构建基块的全合成新策略。到目前为止，它已转变成与jerangolids药效团有关的高级中间体。

  DOI：

  10.1002/ejoc.202000586
• 作为产物：
  描述：

  乙酸乙酯 、 三甲基乙炔基硅 在 magnesium 、 溴丙烷 作用下， 以 四氢呋喃 为溶剂， 反应 2.0h， 以95%的产率得到3-methyl-1,5-bis(trimethylsilyl)penta-1,4-diyn-3-ol
  参考文献：
  名称：

  迈向Jerangolids的全合成-药理学亚基的高级中间体的合成

  摘要：

  在这里，我们提出了一种以跳过的二炔为主要构建基块的全合成新策略。到目前为止，它已转变成与jerangolids药效团有关的高级中间体。

  DOI：

  10.1002/ejoc.202000586

文献信息

• Rhodium-Catalyzed Asymmetric One-Pot Transesterification and [2 + 2 + 2] Cycloaddition Leading to Enantioenriched 3,3-Disubstituted Phthalides
  作者：Ken Tanaka、Takuya Osaka、Keiichi Noguchi、Masao Hirano

  DOI：10.1021/ol070179j

  日期：2007.3.1

  a cationic rhodium(I)/Solphos complex-catalyzed asymmetric one-pot transesterification and [2 + 2 + 2] cycloaddition of 1,6-diyne esters with tertiary propargylic alcohols leading to enantioenriched tricyclic 3,3-disubstituted phthalides. The present method represents a versatile new route to the synthesis of enantioenriched tricyclic 3,3-disubstituted phthalides in view of the easy access to both coupling

  [结构：见文字]。我们已经开发出阳离子铑（I）/ Solphos络合物催化的不对称单锅酯交换反应，以及1,2-二炔酯与叔炔丙醇的[2 + 2 + 2]环加成反应，从而生成对映体富集的三环3,3-二取代的邻苯二甲酸酯。鉴于容易获得两个偶联配偶体，本方法代表了合成对映体富集的三环3，3-二取代邻苯二甲酸酯的通用新途径。
• Selective polymerization of double bonds in 1,5-bis(trimethylsilyl)-3-methylenepentadiyne and 1,5-bis(trimethylsilyl)-3-(2-propylidene)pentadiyne
  作者：Albert H. Alberts

  DOI：10.1021/ja00190a069

  日期：1989.4

  La polymerisation a 80 o C sans catalyseur ni solvant du 1er monomere donne le polydiene correspondant portant des groupes lateraux trimethylsilylethynyl. La polymerisation du 2eme monomere donne un melange d'oligomeres

  La 聚合 a 80 o C sans catalyseur ni solvant du 1er Monomere donne le polydienerespondant portant des groupes lateraux trimethylsilylethynyl。La 聚合 du 2eme Monomere donne un melange d'oligomeres
• Komarov,N.V.; Yarosh,O.G., Journal of general chemistry of the USSR, 1967, vol. 37, p. 247 - 250
  作者：Komarov,N.V.、Yarosh,O.G.

  DOI：——

  日期：——
• Substituent-Dependent Photophysical Properties Due to the Thorpe–Ingold Effect on Foldings of Alternating Substituted Methylene–Diethynylbenzene Copolymers: A Comparison of Carbon versus Silicon Tethers
  作者：Yi-Chung Dzeng、Chi-Ling Huang、Yi-Hung Liu、Tsong-Shin Lim、I-Chia Chen、Tien-Yau Luh

  DOI：10.1021/acs.macromol.5b01820

  日期：2015.12.22

  Alternating tert-butyl- and methyl-substituted alkoxymethylene-diethynylbenzene copolymers with different degrees of polymerization and the corresponding dimers are synthesized. The tert-butyl-substituted polymers show prominent emissions around 350-400 owing to ground state interactions between adjacent chromophores separated by a substituted methylene group. The Thorpe-Ingold effect exerted by the bulky tert-butyl group would compress the bond angle the methylene tether and may alter the, overall folding scaffold of the polymer. The interactions between adjacent chromophores would be significantly enhanced in these tert-butyl-substituted copolymers. On the other hand, the corresponding less bulky, methyl-substituted alkoxymethylene tethered copolymers exhibit emission around 400-450 nm attributed to the through-space interactions between nonadjacent diethynylbenzene chromophores. The, variations of folding nature of these two kinds of copolymers are determined by the size of the substituents, methyl versus tert-butyl, resulting in different photophysical behaviors. The,emission properties of the,methyl-substituted copolymers behave similarly to those of related silylene-tethered copolymers in the literatures, albeit,the relative intensity in the blue light emission is somewhat smaller in methylene-bridged copolymers than in silylene-linked copolymers.
• Towards the Total Synthesis of Jerangolids – Synthesis of an Advanced Intermediate for the Pharmacophore Substructure
  作者：Julian Lenhof、Michael Hutter、Volker Huch、Johann Jauch

  DOI：10.1002/ejoc.202000586

  日期：2020.9.30

  Here, we present a new strategy for the total synthesis based upon a skipped diyne as central building block. This was transformed so far into an advanced intermediate related to the pharmacophore of the jerangolids.

  在这里，我们提出了一种以跳过的二炔为主要构建基块的全合成新策略。到目前为止，它已转变成与jerangolids药效团有关的高级中间体。