5,5-dimethyl-2,2-bis[2-(trimethylsilyl)ethynyl]-1,3-dioxane | 174465-01-1

• 分子结构分类: 有机化合物 - 有机氧化合物
• 英文名称: 5,5-dimethyl-2,2-bis[2-(trimethylsilyl)ethynyl]-1,3-dioxane
• 英文别名: 2-[5,5-Dimethyl-2-(2-trimethylsilylethynyl)-1,3-dioxan-2-yl]ethynyl-trimethylsilane
• CAS: 174465-01-1
• 化学式: C₁₆H₂₈O₂Si₂
• 分子量: 308.568
• InChiKey: UKDPGIQURAGSDC-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  3.52
• 重原子数：
  20
• 可旋转键数：
  4
• 环数：
  1.0
• sp3杂化的碳原子比例：
  0.75
• 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：

  5,5-dimethyl-2,2-bis[2-(trimethylsilyl)ethynyl]-1,3-dioxane 在 copper diacetate 、 水 、 potassium carbonate 作用下， 以 甲醇 、 乙腈 为溶剂， 反应 5.0h， 生成 3,3,14,14,24,24,34,34,44,44,54,54-Dodecamethyl-1,5,12,16,22,26,32,36,42,46,52,56-dodecaoxahexaspiro[5.4.511.4.521.4.531.4.541.4.551.46]hexaconta-7,9,17,19,27,29,37,39,47,49,57,59-dodecayne
  参考文献：
  名称：

  Synthesis and Characterization of Oxygen-Substituted Pericyclynes

  摘要：

  DOI：

  10.1021/jo952087q
• 作为产物：
  描述：

  1,5-bis(trimethylsilyl)penta-1,4-diyn-3-ol 在 manganese(IV) oxide 、 APTS 作用下， 生成 5,5-dimethyl-2,2-bis[2-(trimethylsilyl)ethynyl]-1,3-dioxane
  参考文献：
  名称：

  Synthesis and stereochemical resolution of functional [5]pericyclynes

  摘要：

  Three different kinds of ring carbo-mers of [5]cyclitol ethers were targeted as challenging examples of functional [5]pericyclynes. Three tertiary pentaaryl-carbo-[5]cyclitol methyl ethers were synthesized through a [11 + 4] ring-closing double addition of triphenyl- and tri-p-anisyl-undecatetrayn-diides to dibenzoyl acetylene. These compounds, obtained as oily mixtures of stereoisomers, are stable and can behave as acetylenic ligands of one or two Co-2(CO)(6) units. NMR analysis reveals that the broad diasteroisomeric dispersity of a triether, is consistently reduced in the symmetrized pentaether. Three bis-secondary triaryl-carbo-[5]cyclitol methyl ethers with adjacent CH(OR) vertices were synthesized through a similar [11 + 4] ring-closing process, where the same tetrayn-diides add to both the carbaldehyde ends of the (eta(2)-OCH-C=C-CHO)Co-2(CO)(6) complex. Despite the possibility of tautomeric isomerization, the occurrence of two adjacent bis-propargylic carbinol vertices does not diminish the stability of the [5]pericyclyne framework. Finally, two bis-secondary carbo-[5]cyclitol methyl ethers with non-adjacent CH(OH) vertices were synthesized through an alternative [10 + 5] ring-closing process. The bis-secondary carbo-[5]cyclitols are regarded as isohypsic equivalents of the challenging [C,C](5)carbo-cyclopentadienyl cation. A diphenyl-hexaoxy-[5]pericyclyne with two non-adjacent secondary carbinol vertices was also prepared through a [10 + 5] ring-closing strategy: this molecule is an isohypsic equivalent of the previously calculated zwitterionic carbo-cyclopentadien one, which could be observed as a DCI/NH3-MS fragment after treatment with SnCl2/HCl. Analytical HPLC showed that the C-11 triphenyl-undecatetrayne precursor of the [11 + 4] strategy was obtained as a statistical 1:2:1 mixture of the three possible diastereoisomers. Semi-preparative HPLC allowed for the resolution of this mixture. The pure major diastereoisomer was employed to prepare a partly resolved sample of pentamethoxy-pentaphenyl-[5]pericyclyne. Analytical HPLC showed that the latter corresponds to the statistical distribution of the expected three residual diastereoisomers. Semi-preparative HPLC finally afforded samples of diastereoisomerically pure pentamethoxy[5]pericyclyne as crystalline solids. (C) 2004 Elsevier Ltd. All rights reserved.

  DOI：

  10.1016/j.tet.2004.07.052

文献信息

• Synthesis of New Cyclic Homoconjugated Oligodiacetylenes
  作者：Bernd Leibrock、Otto Vostrowsky、Andreas Hirsch

  DOI：10.1002/1099-0690(200112)2001:23<4401::aid-ejoc4401>3.3.co;2-g

  日期：2001.12
• Synthesis and stereochemical resolution of functional [5]pericyclynes
  作者：Luc Maurette、Christine Tedeschi、Emmanuelle Sermot、Michèle Soleilhavoup、Fatima Hussain、Bruno Donnadieu、Remi Chauvin

  DOI：10.1016/j.tet.2004.07.052

  日期：2004.10

  Three different kinds of ring carbo-mers of [5]cyclitol ethers were targeted as challenging examples of functional [5]pericyclynes. Three tertiary pentaaryl-carbo-[5]cyclitol methyl ethers were synthesized through a [11 + 4] ring-closing double addition of triphenyl- and tri-p-anisyl-undecatetrayn-diides to dibenzoyl acetylene. These compounds, obtained as oily mixtures of stereoisomers, are stable and can behave as acetylenic ligands of one or two Co-2(CO)(6) units. NMR analysis reveals that the broad diasteroisomeric dispersity of a triether, is consistently reduced in the symmetrized pentaether. Three bis-secondary triaryl-carbo-[5]cyclitol methyl ethers with adjacent CH(OR) vertices were synthesized through a similar [11 + 4] ring-closing process, where the same tetrayn-diides add to both the carbaldehyde ends of the (eta(2)-OCH-C=C-CHO)Co-2(CO)(6) complex. Despite the possibility of tautomeric isomerization, the occurrence of two adjacent bis-propargylic carbinol vertices does not diminish the stability of the [5]pericyclyne framework. Finally, two bis-secondary carbo-[5]cyclitol methyl ethers with non-adjacent CH(OH) vertices were synthesized through an alternative [10 + 5] ring-closing process. The bis-secondary carbo-[5]cyclitols are regarded as isohypsic equivalents of the challenging [C,C](5)carbo-cyclopentadienyl cation. A diphenyl-hexaoxy-[5]pericyclyne with two non-adjacent secondary carbinol vertices was also prepared through a [10 + 5] ring-closing strategy: this molecule is an isohypsic equivalent of the previously calculated zwitterionic carbo-cyclopentadien one, which could be observed as a DCI/NH3-MS fragment after treatment with SnCl2/HCl. Analytical HPLC showed that the C-11 triphenyl-undecatetrayne precursor of the [11 + 4] strategy was obtained as a statistical 1:2:1 mixture of the three possible diastereoisomers. Semi-preparative HPLC allowed for the resolution of this mixture. The pure major diastereoisomer was employed to prepare a partly resolved sample of pentamethoxy-pentaphenyl-[5]pericyclyne. Analytical HPLC showed that the latter corresponds to the statistical distribution of the expected three residual diastereoisomers. Semi-preparative HPLC finally afforded samples of diastereoisomerically pure pentamethoxy[5]pericyclyne as crystalline solids. (C) 2004 Elsevier Ltd. All rights reserved.
• Synthesis and Characterization of Oxygen-Substituted Pericyclynes
  作者：Marc Brake、Volker Enkelmann、Uwe H. F. Bunz

  DOI：10.1021/jo952087q

  日期：1996.1.1