1,6-bis(prop-2-ynyloxy)hexa-2,4-diyne | 31334-40-4

• 分子结构分类: 有机化合物 - 有机氧化合物
• 英文名称: 1,6-bis(prop-2-ynyloxy)hexa-2,4-diyne
• 英文别名: 1,6-bis(2-propynyloxy)-2,4-hexadiyne；1,6-Bis-propargyloxy-(hexa-2,4-diin)；1,6-Bis(prop-2-ynoxy)hexa-2,4-diyne
• CAS: 31334-40-4
• 化学式: C₁₂H₁₀O₂
• 分子量: 186.21
• InChiKey: SPOBXMLTBZYXOP-UHFFFAOYSA-N

物化性质

• 沸点：
  313.9±37.0 °C(Predicted)
• 密度：
  1.073±0.06 g/cm3(Predicted)

计算性质

• 辛醇/水分配系数(LogP)：
  0.6
• 重原子数：
  14
• 可旋转键数：
  5
• 环数：
  0.0
• sp3杂化的碳原子比例：
  0.33
• 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：

  1,6-bis(prop-2-ynyloxy)hexa-2,4-diyne 在 bis-triphenylphosphine-palladium(II) chloride 、 copper(l) iodide 、 bis(1,5-cyclooctadiene)rhodium(I) tetrafluoroborate 、 R-(+)-1,1'-联萘-2,2'-双二苯膦 作用下， 以 二氯甲烷 、 三乙胺 为溶剂， 反应 32.0h， 生成 4-phenyl-7-[3-(3-phenylprop-2-ynyloxy)-prop-1-ynyl]-1,3-dihydroisobenzofuran-5,6-dicarboxylic acid dimethyl ester
  参考文献：
  名称：

  通过铑催化的双[2 + 2 + 2]环加成反应，对映体选择性合成四邻位取代的轴向手性联芳基。

  摘要：

  [反应：见正文]我们已经通过铑催化的双[2 + 2 + 2]环加成反应（高达99％ee）建立了C2对称和不对称的四邻位取代的轴向手性联芳基的对映选择性合成。鉴于从容易获得的炔烃开始一步接触底物二炔和四炔，该方法成为制备对映体富集的四邻位取代的轴向手性联芳基的一种有吸引力的新途径。

  DOI：

  10.1021/ol0611550
• 作为产物：
  描述：

  2-丙炔-1-醇 、 2,4-己二炔-1,6-二醇 在 hexacarbonyldicobalt 、 三氟化硼乙醚 、 ammonium cerium(IV) nitrate 作用下， 以 二氯甲烷 、 丙酮 为溶剂， 反应 1.17h， 以81%的产率得到1,6-bis(prop-2-ynyloxy)hexa-2,4-diyne
  参考文献：
  名称：

  Double Cationic Propargylation:  From Linear to Polycyclic Ethers

  摘要：

  [GRAPHICS]The trapping of cations generated from Co-2(CO)(6)-bispropargylic alcohols provided diethers in good yield. The procedure is also valid when two vicinal acetylenes are present. The methodology can be applied to the synthesis of symmetrical or unsymmetrical linear or cyclic propargylic ethers. The use of substrates with a stereochemically defined secondary nucleophilic alcohol provided cyclic ethers with a high degree of stereocontrol.

  DOI：

  10.1021/ol0164987

文献信息

• Tetradehydro-Diels–Alder Reactions of Flexible Arylalkynes via Folding Inside a Molecular Cage
  作者：Georgi R. Genov、Hiroki Takezawa、Harumi Hayakawa、Makoto Fujita

  DOI：10.1021/jacs.3c06301

  日期：2023.8.9

  employed substrates allows for efficient encapsulation within the host cavity. The rate of thermal cyclization of the encapsulated guest was found to be greatly enhanced, and high product selectivity for an unsymmetrical substrate was observed. The efficiency of this system relies on the precise conformational control of the substrate within the confined space of the host cage.

  四氢-狄尔斯-阿尔德 (TDDA) 反应是一种有用的转化，可在单个合成步骤中从简单的线性前体快速组装多环支架。然而，该反应需要仔细的底物设计和苛刻的反应条件，以克服这种转化固有的熵成本。在此，我们报告了自组装 Pd 6 L 4笼内有效的位点选择性 TDDA 转化。尽管尺寸很大，但所使用的基板的灵活性允许在主体腔内进行有效的封装。发现封装客体的热环化速率大大提高，并且观察到对不对称基材的高产物选择性。该系统的效率依赖于宿主笼有限空间内底物的精确构象控制。
• Metathesis and Metallotropy:  A Versatile Combination for the Synthesis of Oligoenynes
  作者：Mansuk Kim、Daesung Lee

  DOI：10.1021/ja057153c

  日期：2005.12.1

  We have demonstrated that the combined use of enyne metathesis and metallotropic [1,3]-shift of the corresponding alkynyl ruthenium carbenes is a powerful synthetic tool to construct oligoenynes. In this reaction, alkynyl carbene intermediates formed from an initial ring-closing metathesis reaction (RCM) undergo repetitive [1,3]-shifts and RCMs to give the final products. Linear poly-1,3-diynes containing repeating functionality of the type -[XCH2CCCCCH2]n- generated long-chain conjugated oligoenynes up to n = 5.
• Asymmetric Synthesis and Photophysical Properties of Benzopyrano- or Naphthopyrano-Fused Helical Phosphafluorenes
  作者：Naohiro Fukawa、Takuya Osaka、Keiichi Noguchi、Ken Tanaka

  DOI：10.1021/ol100227k

  日期：2010.3.19

  Enantioenriched benzopyrano- and naphthopyrano-fused helical phosphafluorenes have been synthesized by the rhodium-catalyzed enantioselective double [2 + 2 + 2] cycloaddition of dialkynyl phosphorus compounds with phenol- or naphthol-linked tetraynes. Photophysical properties of these phosphafluorenes are also disclosed.
• Double Cationic Propargylation:  From Linear to Polycyclic Ethers
  作者：David Díaz、Tomás Martín、Víctor S. Martín

  DOI：10.1021/ol0164987

  日期：2001.10.1

  [GRAPHICS]The trapping of cations generated from Co-2(CO)(6)-bispropargylic alcohols provided diethers in good yield. The procedure is also valid when two vicinal acetylenes are present. The methodology can be applied to the synthesis of symmetrical or unsymmetrical linear or cyclic propargylic ethers. The use of substrates with a stereochemically defined secondary nucleophilic alcohol provided cyclic ethers with a high degree of stereocontrol.
• Enantioselective Synthesis of Tetra-<i>ortho</i>-Substituted Axially Chiral Biaryls through Rhodium-Catalyzed Double [2 + 2 + 2] Cycloaddition
  作者：Goushi Nishida、Nanami Suzuki、Keiichi Noguchi、Ken Tanaka

  DOI：10.1021/ol0611550

  日期：2006.8.1

  [reaction: see text] We have established an enantioselective synthesis of both C2 symmetric and unsymmetric tetra-ortho-substituted axially chiral biaryls through rhodium-catalyzed double [2 + 2 + 2] cycloaddition (up to >99% ee). This method serves as an attractive new route to enantioenriched tetra-ortho-substituted axially chiral biaryls in view of the one-step access to substrate diynes and tetraynes

  [反应：见正文]我们已经通过铑催化的双[2 + 2 + 2]环加成反应（高达99％ee）建立了C2对称和不对称的四邻位取代的轴向手性联芳基的对映选择性合成。鉴于从容易获得的炔烃开始一步接触底物二炔和四炔，该方法成为制备对映体富集的四邻位取代的轴向手性联芳基的一种有吸引力的新途径。