2-(But-2-yn-1-yl)-1-{2-[2-(but-3-yn-1-yl)phenyl]ethyn-1-yl}naphthalene | 223596-88-1

• 分子结构分类: 有机化合物 - 苯类化合物 - 萘
• 英文名称: 2-(But-2-yn-1-yl)-1-{2-[2-(but-3-yn-1-yl)phenyl]ethyn-1-yl}naphthalene
• 英文别名: 2-But-3-ynyl-1-[2-(2-but-3-ynylphenyl)ethynyl]naphthalene
• CAS: 223596-88-1
• 化学式: C₂₆H₂₀
• 分子量: 332.445
• InChiKey: OLLLYKBRRNOOCU-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  6.9
• 重原子数：
  26
• 可旋转键数：
  6
• 环数：
  3.0
• sp3杂化的碳原子比例：
  0.15
• 拓扑面积：
  0
• 氢给体数：
  0
• 氢受体数：
  0

反应信息

• 作为反应物：
  描述：

  2-(But-2-yn-1-yl)-1-{2-[2-(but-3-yn-1-yl)phenyl]ethyn-1-yl}naphthalene 在 bis(1,5-cyclooctadiene)nickel (0) 作用下， 以 四氢呋喃 为溶剂， 反应 0.08h， 以75%的产率得到tetrahydro<6>helicene
  参考文献：
  名称：

  Synthesis of Helicene Scaffolds via [2+2+2] Cycloisomerization of Aromatic Triynes

  摘要：

  Triynes R-C≡C-CH2CH2-Ar-C≡C-Ar'-CH2CH2-C≡C-R经过Co(I)-或Ni(0)-介导的分子内[2+2+2]环异构化反应，产生相应的四氢五环螺花烯、四氢六环螺花烯和四氢七环螺花烯，收率良好至适中。该反应容忍在侧链乙炔基团上具有各种取代基（R = H、CH3、三甲基硅基，但不是三异丙基硅基）和芳香部分中的氟原子。相比之下，在Rh(I)或Pd(0)催化下，带有CH2OCH2连接基的三炔失去了侧链丙炔基团，优先形成了芳香螺环缩酮。

  DOI：

  10.1135/cccc20030917
• 作为产物：
  描述：

  2-(Bromomethyl)-1-{2-[2-(bromomethyl)phenyl]ethyn-1-yl}naphthalene 在 四丁基氟化铵 作用下， 以 四氢呋喃 为溶剂， 反应 2.0h， 生成 2-(But-2-yn-1-yl)-1-{2-[2-(but-3-yn-1-yl)phenyl]ethyn-1-yl}naphthalene
  参考文献：
  名称：

  过渡金属催化合成[5]-，[6]-和[7] hel烯的四氢衍生物

  摘要：

  通过在CpCo（CO）2 / PPh 3或Ni（cod）2 /下将适当的三炔进行分子内[2 + 2 + 2]环异构化，可以轻松制备[5]-，[6]-和[7]螺旋的四氢类似物。PPh 3催化。这种非光化学方法学允许使用Ni（cod）2 /（S）-（-）-MOP催化系统对映选择性合成螺旋骨架。与DDQ反应时，四氢[5]]烯转化为[5] hel烯。

  DOI：

  10.1016/s0040-4039(99)00099-4

文献信息

• Transition metal catalysed synthesis of tetrahydro derivatives of [5]-, [6]- and [7]helicene
  作者：Irena G Stará、Ivo Starý、Adrian Kollárovič、Filip Teplý、Štěpán Vyskočil、David Šaman

  DOI：10.1016/s0040-4039(99)00099-4

  日期：1999.3

  analogues of [5]-, [6]- and [7]helicene have been easily prepared by intramolecular [2+2+2] cycloisomerization of appropriate triynes under CpCo(CO)2/PPh3 or Ni(cod)2/PPh3 catalysis. This nonphotochemical methodology allows enantioselective synthesis of a helical skeleton employing the Ni(cod)2/(S)-(−)-MOP catalytic system. On reaction with DDQ, tetrahydro[5]helicene was transformed to [5]helicene.

  通过在CpCo（CO）2 / PPh 3或Ni（cod）2 /下将适当的三炔进行分子内[2 + 2 + 2]环异构化，可以轻松制备[5]-，[6]-和[7]螺旋的四氢类似物。PPh 3催化。这种非光化学方法学允许使用Ni（cod）2 /（S）-（-）-MOP催化系统对映选择性合成螺旋骨架。与DDQ反应时，四氢[5]]烯转化为[5] hel烯。
• Enantioselective [2+2+2] cycloisomerisation of alkynes in the synthesis of helicenes: The search for effective chiral ligands
  作者：Irena G. Stará、Angelina Andronova、Adrian Kollárovič、Štěpán Vyskočil、Sylvain Jugé、Guy C. Lloyd-Jones、Patrick J. Guiry、Ivo Starý

  DOI：10.1135/cccc2011177

  日期：——

  The enantioselective [2+2+2] cycloisomerisation of the aromatic triynes under nickel(0) catalysis to afford nonracemic [6]- and [7]helicene derivatives has been systematically studied. A collection of mono- and bidentate phosphines, phosphites, phosphinites and phosphinous amides possessing stereogenic units such as chiral centre, axis or plane (or their combinations) has been tested and axially chiral binaphthyl-derived monodentate MOP-type phosphine ligands were the optimal class of ligands. Nickel complexes of these ligands afforded nonracemic tetrahydro[6]helicene in up to 64% ee in a model reaction.

  芳香族三炔烃在镍（0）催化下进行立体选择性的[2+2+2]环异构化反应，生成非拉克米的[6]-和[7]螺芴衍生物已经被系统研究。一系列具有手性中心、轴或平面（或它们的组合）的单齿和双齿膦、膦酸酯、膦酸酯和膦酰胺已经被测试，其中轴手性的双齿MOP型膦配体是最佳的配体类别。这些配体的镍配合物在模型反应中生成非拉克米的四氢[6]螺芴，其对映选择性可高达64% ee。
• Chiral cobaltI and nickel0 complexes in the synthesis of nonracemic helicenes through the enantioselective [2 + 2 + 2] cyclotrimerisation of alkynes
  作者：Barbara Heller、Marko Hapke、Christine Fischer、Angelina Andronova、Ivo Starý、Irena G. Stará

  DOI：10.1016/j.jorganchem.2012.07.005

  日期：2013.1

  The enantioselective intramolecular [2 + 2 + 2] cycloisomerisation of triynes under catalysis by chiral transition-metal complexes (Co-I, Ni-0) in order to receive nonracemic helicene derivatives was explored. The use of the chiral neomenthylindene Co-I complex led to a moderate 25% ee of tetrahydro[6] helicene, which was the first example of such a reaction catalysed by the chiral Co-I complex. The alternative Ni-0 catalysis employing privileged axially chiral monophosphines such as (-)-(aS)-NAPHEP led to tetrahydro [6] helicene with 64% ee, which is among the highest enantiomeric excesses so far observed for this Ni-0-catalysed reaction. (C) 2012 Elsevier B. V. All rights reserved.
• Synthesis of Aromatic Triynes as Precursors to Helicene Derivatives
  作者：Irena G. Stará、Adrian Kollárovič、Filip Teplý、Ivo Starý、David Šaman、Pavel Fiedler

  DOI：10.1135/cccc20000577

  日期：——

  A general and versatile synthetic approach to a broad series of aromatic triynes as precursors to helicene derivatives has been developed. Employing a set of simple tools, triynes comprising the (phenylethynyl)benzene, 1-(phenylethynyl)naphthalene, and 1-(1-naphthylethynyl)- naphthalene moiety have been prepared in good to excellent yields throughout the whole reaction sequence. The methodology allows constructing various types of a junction between the central diarylacetylene moiety and the attached acetylene units to get the target triynes of general formula R-C≡C-CH₂-X-CH₂-Ar-C≡C-Ar'-CH₂-X-CH₂-C≡C-R or R-C≡C-CH₂CH₂-Ar-C≡C-Ar'-CH₂CH₂-C≡C-R (R = H, CH₃, TMS, or TIPS; X = O, NTs, or C(CO₂CH₃)₂; Ar/Ar' = 2-phenylene or 2-naphthylene).

  已经开发出一种通用且多功能的合成方法，用于制备芳香三炔作为螺环衍生物的前体。利用一组简单的工具，在整个反应序列中成功制备了包含苯基乙炔基苯、1-(苯基乙炔基)萘和1-(1-萘基乙炔基)-萘基的三炔，收率良好至优良。该方法允许在中心二芳基乙炔基和附加的乙炔单元之间构建各种类型的连接点，以获得通用公式 R-C≡C-CH₂-X-CH₂-Ar-C≡C-Ar'-CH₂-X-CH₂-C≡C-R 或 R-C≡C-CH₂CH₂-Ar-C≡C-Ar'-CH₂CH₂-C≡C-R（R = H、CH₃、TMS 或 TIPS；X = O、NTs 或 C(CO₂CH₃)₂；Ar/Ar' = 2-苯基或2-萘基）。
• Synthesis of Helicene Scaffolds via [2+2+2] Cycloisomerization of Aromatic Triynes
  作者：Irena G. Stará、Ivo Starý、Adrian Kollárovič、Filip Teplý、David Šaman、Pavel Fiedler

  DOI：10.1135/cccc20030917

  日期：——

  Triynes R-C≡C-CH₂CH₂-Ar-C≡C-Ar'-CH₂CH₂-C≡C-R were subjected to Co(I)- or Ni(0)-mediated intramolecular [2+2+2] cycloisomerization to provide corresponding tetrahydropentahelicene, tetrahydrohexahelicene, and tetrahydroheptahelicene in good to moderate yields. The reaction tolerates various substituents at pendant acetylene moieties (R = H, CH₃, trimethylsilyl, not triisopropylsilyl) and fluorine in an aromatic part. By contrast, under Rh(I) or Pd(0) catalysis, triyne with the CH₂OCH₂ tether lost pendant propargyl moieties and an aromatic spiroketal was formed preferentially.

  Triynes R-C≡C-CH2CH2-Ar-C≡C-Ar'-CH2CH2-C≡C-R经过Co(I)-或Ni(0)-介导的分子内[2+2+2]环异构化反应，产生相应的四氢五环螺花烯、四氢六环螺花烯和四氢七环螺花烯，收率良好至适中。该反应容忍在侧链乙炔基团上具有各种取代基（R = H、CH3、三甲基硅基，但不是三异丙基硅基）和芳香部分中的氟原子。相比之下，在Rh(I)或Pd(0)催化下，带有CH2OCH2连接基的三炔失去了侧链丙炔基团，优先形成了芳香螺环缩酮。