3,6,9-trimethoxy-3,6,9-tris(4-methoxyphenyl)undeca-1,4,7,10-tetrayne | 801287-55-8

• 分子结构分类: 有机化合物 - 苯丙烷和聚酮 - 二芳基庚烷
• 英文名称: 3,6,9-trimethoxy-3,6,9-tris(4-methoxyphenyl)undeca-1,4,7,10-tetrayne
• 英文别名: 1-Methoxy-4-[3,6,9-trimethoxy-3,9-bis(4-methoxyphenyl)undeca-1,4,7,10-tetrayn-6-yl]benzene；1-methoxy-4-[3,6,9-trimethoxy-3,9-bis(4-methoxyphenyl)undeca-1,4,7,10-tetrayn-6-yl]benzene
• CAS: 801287-55-8
• 化学式: C₃₅H₃₂O₆
• 分子量: 548.635
• InChiKey: XHMHQJKWWIOBLL-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  5.1
• 重原子数：
  41
• 可旋转键数：
  15
• 环数：
  3.0
• sp3杂化的碳原子比例：
  0.26
• 拓扑面积：
  55.4
• 氢给体数：
  0
• 氢受体数：
  6

反应信息

• 作为反应物：
  描述：

  3,6,9-trimethoxy-3,6,9-tris(4-methoxyphenyl)undeca-1,4,7,10-tetrayne 在 正丁基锂 、 hexacarbonyldicobalt 作用下， 以 四氢呋喃 、 正己烷 、 二甲基亚砜 为溶剂， 反应 3.0h， 生成 1,4,7,10-pentamethoxy-1,4,13-tris(4-methoxyphenyl)cyclopentadeca-2,5,8,11,14-pentayne
  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
• 作为产物：
  描述：

  1,11-bis(trimethylsilyl)-3,9-dimethoxy-3,6,9-tris(4-methoxyphenyl)undeca-1,4,7,10-tetrayn-6-ol 在 正丁基锂 、 potassium carbonate 作用下， 以 四氢呋喃 、 甲醇 、 正己烷 、 二甲基亚砜 为溶剂， 反应 5.0h， 生成 3,6,9-trimethoxy-3,6,9-tris(4-methoxyphenyl)undeca-1,4,7,10-tetrayne
  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 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.