[4-(1-ethynylnaphthalen-2-yl)but-1-yn-1-yl][tri(propan-2-yl)]silane | 566912-09-2

• 分子结构分类: 有机化合物 - 苯类化合物 - 萘
• 英文名称: [4-(1-ethynylnaphthalen-2-yl)but-1-yn-1-yl][tri(propan-2-yl)]silane
• 英文别名: (4-(1-ethynylnaphthalen-2-yl)but-1-ynyl)triisopropylsilane；[4-(1-ethynyl-2-naphthyl)-1-butynyl](triisopropyl)silane；4-(1-Ethynylnaphthalen-2-yl)but-1-ynyl-tri(propan-2-yl)silane
• CAS: 566912-09-2
• 化学式: C₂₅H₃₂Si
• 分子量: 360.615
• InChiKey: GMPVVHCMVMCCAS-UHFFFAOYSA-N

物化性质

• 沸点：
  452.8±38.0 °C(Predicted)
• 密度：
  0.96±0.1 g/cm3(Predicted)

计算性质

• 辛醇/水分配系数(LogP)：
  6.98
• 重原子数：
  26
• 可旋转键数：
  7
• 环数：
  2.0
• sp3杂化的碳原子比例：
  0.44
• 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：

  [4-(1-ethynylnaphthalen-2-yl)but-1-yn-1-yl][tri(propan-2-yl)]silane 在 吡啶 、 4-二甲氨基吡啶 、 氢化镓 、 bis-triphenylphosphine-palladium(II) chloride 、 indium 、 copper(l) iodide 、 四丁基氟化铵 、 三乙胺 作用下， 以 四氢呋喃 为溶剂， 反应 4.33h， 生成
  参考文献：
  名称：

  炔烃的[2+2+2]环异构化合成(二)硫杂螺烯和二硫代苯螺烯

  摘要：

  通过分子内炔烃 [2+ 2+2]环异构化。研究了它们的结构、化学和物理化学性质，例如晶体堆积、氧化、外消旋化阻隔、自发薄膜转变或电化学行为，并与母体全碳螺烯和二苯并螺烯各自的性质进行了比较。

  DOI：

  10.1002/hlca.202100225
• 作为产物：
  描述：

  triisopropyl(4-{1-[(trimethylsilyl)ethynyl]-2-naphthyl}-1-butynyl)silane 在 sodium methylate 作用下， 以 甲醇 为溶剂， 反应 16.0h， 以99%的产率得到[4-(1-ethynylnaphthalen-2-yl)but-1-yn-1-yl][tri(propan-2-yl)]silane
  参考文献：
  名称：

  Synthesis of 3-Hexahelicenol and Its Transformation to 3-Hexahelicenylamines, Diphenylphosphine, Methyl Carboxylate, and Dimethylthiocarbamate

  摘要：

  A nonphotochemical synthetic route to 3-hexahelicenol is reported. It involves a key [2+2+2] cycloisomerization of CH3O-substituted triyne that is readily available from 1-methoxy-3-methylbenzene and 1-bromo-2-(bromomethyl)naphthalene. Further functional group transformations led to 3-CO2CH3, 3-NH2, 3-PPh2, and 3-SC(O)N(CH3)(2) substituted hexahelicenes.

  DOI：

  10.1021/jo034369t

文献信息

• Synthesis of Long Oxahelicenes by Polycyclization in a Flow Reactor
  作者：Jindřich Nejedlý、Michal Šámal、Jiří Rybáček、Miroslava Tobrmanová、Florence Szydlo、Christophe Coudret、Maria Neumeier、Jaroslav Vacek、Jana Vacek Chocholoušová、Miloš Buděšínský、David Šaman、Lucie Bednárová、Ladislav Sieger、Irena G. Stará、Ivo Starý

  DOI：10.1002/anie.201700341

  日期：2017.5.15

  series of oxahelicenes composed of ortho/meta‐annulated benzene/pyridine and 2H‐pyran rings were synthesized on the basis of the cobalt(I)‐mediated (or rhodium(I)‐ or nickel(0)‐mediated) double, triple, or quadruple [2+2+2] cycloisomerization of branched aromatic hexa‐, nona‐, or dodecaynes, thus allowing the construction of 6, 9, or 12 rings in a single operation. The use of a flow reactor was found

  由邻位/间位环苯/吡啶和2 H组成的一系列氧杂泛烯吡喃环是在分支的芳族六环的钴（I）介导的（或铑（I）-或镍（0）介导的）[2 + 2 + 2]环异构化的两倍，三重或四重合成的基础上合成的，九碳烯或十二碳烯，因此可以在一次操作中构建6、9或12个环。发现使用流动反应器对于多环化反应是有益的。一些寡聚体中存在的立体异构中心控制了螺旋折叠，从而最终获得了对映体和非对映体纯形式的最终氧杂[9]-，[13]-，[17]-和[19]螺旋。具体来说，氧杂[19]螺旋烯在螺旋烯骨架的长度上打破了目前的记录。单分子电导率通过吡a醇[9]螺旋的机械可控断裂连接方法进行了研究。
• A Convenient Route to 2-Hydroxy- and 2,15-Dihydroxyhexahelicene
  作者：Filip Teplý、Irena G. Stará、Ivo Starý、Adrian Kollárovič、Daniel Luštinec、Zuzana Krausová、David Šaman、Pavel Fiedler

  DOI：10.1002/ejoc.200700381

  日期：2007.9

  2-Hydroxy- and 2,15-dihydroxyhexahelicene were synthesised from simple benzene and naphthalene building blocks by intramolecular CoI- or Ni0-catalysed [2+2+2] cycloisomerisation of CH3O-substituted aromatic triynes. This approach avoids vexing photodehydrocyclisation of stilbene-type precursors, providing thus a useful alternative to classical procedures. (© Wiley-VCH Verlag GmbH & Co. KGaA, 69451

  通过分子内 CoI 或 Ni0 催化的 CH3O 取代的芳族三炔的 [2+2+2] 环异构化，从简单的苯和萘结构单元合成了 2-羟基和 2,15-二羟基六螺旋。这种方法避免了二苯乙烯型前体令人烦恼的光脱氢环化，从而为经典程序提供了一种有用的替代方法。(© Wiley-VCH Verlag GmbH & Co. KGaA, 69451 Weinheim, Germany, 2007)
• Synthesis of Methoxy Substituted Centrally Chiral Triynes as Precursors of Functionalised Nonracemic Helicene-Like Compounds
  作者：Zuzana Krausová、Petr Sehnal、Filip Teplý、Irena G. Stará、Ivo Starý、David Šaman、Josef Cvačka、Pavel Fiedler

  DOI：10.1135/cccc20071499

  日期：——

  A modular synthesis of a series of methoxy substituted optically pure aromatic triynes (-)-(S)-5-9 and (-)-(R)-10 is presented. It relies on key operations such as substitution of benzylic bromine with an alkoxy group and aryl-alkyne coupling reaction to combine appropriate methoxy substituted benzene/naphthalene building blocks and chiral alkynol synthons such as (-)-(2S)-but-3-yn-2-ol and (-)-(1R)-1-phenylprop-2-yn-1-ol. The triyne molecules comprise a diphenylacetylene, 1-(phenylethynyl)naphthalene or 1,1'-ethyne-1,2-diyldinaphthalene core unit. They are intended to serve as [2+2+2] cyclisation precursors of methoxy substituted nonracemic helicene-like compounds with a penta-, hexa- and heptacyclic helical scaffold.

  提出了一种甲氧基取代的光学纯芳香三炔烃系列（-）-S-5-9和（-）-R-10的模块化合成方法。该方法依赖于关键操作，如用烷氧基取代苄溴基和芳基-炔基偶联反应，将适当的甲氧基取代苯/萘构建基与手性炔醇合成物（如（-）-（2S）-丁-3-炔-2-醇和（-）-（1R）-苯基丙-2-炔-1-醇）结合。三炔烃分子包括二苯基乙炔、1-(苯乙炔基)萘或1,1'-乙炔-1,2-二基二萘核心单元。它们旨在作为甲氧基取代的非拉克米螺旋烯类化合物的[2+2+2]环化前体，具有五、六和七环螺旋骨架。
• The quest for alternative routes to racemic and nonracemic azahelicene derivatives
  作者：Angelina Andronova、Florence Szydlo、Filip Teplý、Miroslava Tobrmanová、Amandine Volot、Irena G. Stará、Ivo Starý、Lubomír Rulíšek、David Šaman、Josef Cvačka、Pavel Fiedler、Pavel Vojtíšek

  DOI：10.1135/cccc2008180

  日期：——

  A series of diverse aromatic azadienetriyne and azatriynes was synthesised. These compounds were subjected to transition metal-mediated [2+2+2] cycloisomerisation to form pentacyclic or hexacyclic helically chiral azahelicene or azahelicene-like structures mostly in moderate yields. Introducing stereogenic centre(s) into selected azatriynes, cyclisation proceeded in a stereoselective fashion providing aza[5]helicenes or aza[6]helicene-like compounds in up to a 100:0 diastereomeric ratio. Gibbs energy differences between corresponding pairs of diastereomers (calculated at the DFT(B3LYP)/TZV+P level) were in good agreement with the experimental data and allowed for the prediction of the stereochemical outcome of the reaction. This study presents for the first time asymmetric synthesis of azahelicene derivatives in high optical purities.

  合成了一系列多样的芳香性的偶氮二炔和偶氮三炔化合物。这些化合物经过过渡金属介导的[2+2+2]环异构化反应，形成了大部分处于中等产率下的五环或六环螺旋手性氮杂螺芴或氮杂螺芴类结构。在选定的偶氮三炔中引入立体异构中心后，环化反应以立体选择性的方式进行，提供了最高达到100:0的对映异构比例的氮杂[5]螺芴或氮杂[6]螺芴类化合物。在对应的对映异构体对之间的吉布斯自由能差异（在DFT(B3LYP)/TZV+P水平计算）与实验数据非常吻合，并可用于预测反应的立体化学结果。这项研究首次展示了高光学纯度下氮杂螺芴衍生物的不对称合成。
• Synthetic Studies Toward Chiral Aromatic Triynes as Key Substrates for the Asymmetric Synthesis of Helicene-Like Molecules
  作者：Zuzana Alexandrová、Irena G. Stará、Petr Sehnal、Filip Teplý、Ivo Starý、David Šaman、Pavel Fiedler

  DOI：10.1135/cccc20042193

  日期：——

  We have developed the synthesis of model nonracemic aromatic triynes (-)-(S)-1-4 containing the 1-[2-(but-3-yn-1-yl)-1-naphthyl]ethynyl}-2-[((S)-1-methylprop-2-yn-1-yl)oxy]- methyl}naphthalene unit. The common 1,2-di(2-substituted-1-naphthyl)acetylene part was constructed via Sonogashira coupling of appropriate 1-iodonaphthalenes with 1-ethynylnaphthalenes both bearing tethered acetylene units in positions 2. The chirality of triynes (-)-(S)-1-4 was introduced by incorporating commercially available (-)-(S)-but-3-yn-2-ol (10) into tethered acetylene units. The nonracemic triynes are intended to be used as substrates in stereoselective [2+2+2] triyne cycloisomerization catalyzed by transition metal complexes.

  我们已经开发了模型非拉克米芳香三炔烃的合成，其中包含1-[2-(丁-3-炔-1-基)-1-萘基]乙炔基}-2-[((S)-1-甲基丙-2-炔基)氧基]-甲基}萘单元。常见的1,2-二(2-取代-1-萘基)乙炔部分是通过适当的1-碘萘与带有位置2上乙炔基的1-乙炔基萘的Sonogashira偶联构建的。三炔烃(-)-(S)-1-4的手性是通过将市售的(-)-(S)-丁-3-炔-2-醇(10)并入带有乙炔基的单元引入的。非拉克米三炔烃旨在用作过渡金属配合物催化的立体选择性[2+2+2]三炔环异构化反应的底物。