1-cyclohexyl-4,4-bis(methoxycarbonyl)-1(E)-hepten-6-yne | 95123-99-2

• 分子结构分类: 有机化合物 - 脂质和类脂质分子 - 脂肪酰基
• 英文名称: 1-cyclohexyl-4,4-bis(methoxycarbonyl)-1(E)-hepten-6-yne
• 英文别名: (E)-1-cyclohexyl-4,4-dicarbomethoxyhept-1-ene-6-yne；4,4-bis(methoxycarbonyl)-7-cyclohexyl-hept-6(E)-en-1-yne；dimethyl 2-[(E)-3-cyclohexylprop-2-enyl]-2-prop-2-ynylpropanedioate
• CAS: 95123-99-2
• 化学式: C₁₇H₂₄O₄
• 分子量: 292.375
• InChiKey: YYVKJUQTMBYEIL-DHZHZOJOSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  4.1
• 重原子数：
  21
• 可旋转键数：
  8
• 环数：
  1.0
• sp3杂化的碳原子比例：
  0.65
• 拓扑面积：
  52.6
• 氢给体数：
  0
• 氢受体数：
  4

反应信息

• 作为反应物：
  描述：

  1-cyclohexyl-4,4-bis(methoxycarbonyl)-1(E)-hepten-6-yne 在 tris(dibenzylideneacetone)dipalladium(0) chloroform complex 、 三(邻甲基苯基)磷 polymethylhydrosiloxane 、 溶剂黄146 作用下， 以 苯 为溶剂， 反应 6.0h， 以96%的产率得到3-Cyclohexylmethyl-4-methylene-cyclopentane-1,1-dicarboxylic acid dimethyl ester
  参考文献：
  名称：

  Reductive cyclization of 1,6- and 1,7-enynes

  摘要：

  DOI：

  10.1021/ja00244a059
• 作为产物：
  描述：

  环己烷基甲醛 在 四(三苯基膦)钯 、 sodium hydride 、 三苯基膦 作用下， 反应 9.75h， 生成 1-cyclohexyl-4,4-bis(methoxycarbonyl)-1(E)-hepten-6-yne
  参考文献：
  名称：

  Pd-Catalyzed Cycloisomerization to 1,2- Dialkylidenecycloalkanes. 1

  摘要：

  Enhancing synthetic efficiency requires the development of synthetic reactions that, to the extent possible, are simple additions wherein everything else is required only in catalytic amounts. The Alder ene reaction constitutes a classical reaction that meets this requirement that has much unrealized potential. A transition-metal-catalyzed version helps to increase that potential by permitting this reaction to proceed under mild conditions. A significant benefit of transition metal catalysis is the feasibility of diverting the reaction along pathways not feasible under thermal conditions. The synthesis of 1,3-dienes rather than 1,4-dienes is a very important diversion because of the utility of 1,3-dienes as reaction partners in the Diels-Alder reaction, another highly atom economical process. A catalyst derived from palladium acetate cycloisomerizes 1,6- and 1,7-enynes to dialkylidenecyclopentanes and -cyclohexanes. 1,3-Diene formation is favored over the Alder ene process by both steric and electronic effects. The reaction is highly chemoselective-tolerating a wide diversity of functionality including hydroxyl groups, ketones, esters, alkynyl and enol ethers, alkynyl and vinyl silanes, and enones. Many of the substrates are available by palladium-catalyzed alkylation reactions-highlighting the effectiveness of palladium catalyzed methodology in organic synthesis. The atom-economical nature of these reactions combined with the Diels-Alder reaction permit butadiene and dimethyl propargylmalonate to be molded into a polyhydro-as-indacene. The mechanism of this reaction may involve a tautomerization of an enyne-Pd(+2) complex to a pallada(+4)cyclopentene intermediate as a key step.

  DOI：

  10.1021/ja00089a015

文献信息

• Mechanistic Dichotomy in CpRu(CH₃CN)₃PF₆ Catalyzed Enyne Cycloisomerizations
  作者：Barry M. Trost、F. Dean Toste

  DOI：10.1021/ja012450c

  日期：2002.5.1

  Enynes are easily accessible building blocks as a result of the rich chemistry of alkynes and thus represent attractive substrates for ring formation. A ruthenium catalyst for cycloisomerization effects such reaction of 1,6- and 1,7-enynes typically at room temperature in acetone or DMF under neutral conditions. The reaction is effective for forming five- and six-membered rings of widely divergent

  由于炔烃的丰富化学性质，炔烃很容易获得结构单元，因此是形成环的有吸引力的底物。用于环异构化的钌催化剂通常在室温下在丙酮或 DMF 中在中性条件下实现 1,6- 和 1,7- 烯炔的此类反应。该反应可有效形成具有广泛发散结构的五元和六元环。炔烃可以带有供选和退选取代基。烯烃可以是二或三取代的。然而，在炔酸的炔丙基位置引入四元中心完全改变了反应的性质。在 1,6-烯酸酯的情况下，在同样温和的条件下以优异的产率形成七元环。提供的证据表明机制发生了完全变化。在前一种情况下，反应涉及钌环戊烯的中间体。在后一种情况下，提出了一个 CH 插入以形成 π-烯丙基钌中间体，并且...
• Ruthenium-Catalyzed Cycloisomerizations of 1,6- and 1,7-Enynes
  作者：Barry M. Trost、F. Dean Toste

  DOI：10.1021/ja993401r

  日期：2000.2.1
• Trost, Barry M.; Lautens; Chan, Journal of the American Chemical Society, 1991, vol. 113, # 2, p. 636 - 644
  作者：Trost, Barry M.、Lautens、Chan、Jebaratnam、Mueller

  DOI：——

  日期：——
• Pd-Catalyzed Cycloisomerization to 1,2-Dialkylidenecycloalkanes. 2. Alternative Catalyst System
  作者：Barry M. Trost、Donna L. Romero、Frode Rise

  DOI：10.1021/ja00089a016

  日期：1994.5

  The mechanisms by which palladium complexes may catalyze the cycloisomerization of 1,6- and 1,7-enynes to dialkylidenecycloalkanes were probed by exploring a catalyst system different than a ligated palladium acetate which previously has proven to be successful. Although carboxylic acids showed no discernible interaction with palladium(0) complexes, this combination proved to be a powerful catalyst system to effect this cycloisomerization. The fact that the two catalyst systems do not have the same reactivity profile suggests this new catalyst system may operate by a different mechanism. Evidence supporting a pathway invoking formation of a hydridopalladium acetate followed by hydropalladation as initiation is presented. Steric and electronic effects direct the regioselectivity of the termination step to form either 1,3- or 1,4-diene products. The 1,3-diene products participate exceedingly well in Diels-Alder reactions, both inter- and intramolecularly. The presence of an oxygen substituent at the position allylic to the diene served as both a regiochemical control element for the palladium-catalyzed cycloisomerization and a diastereochemical control element for the Diels-Alder reaction. The net result of these two steps, the first of which is a catalyzed isomerization and the second an addition, is a highly efficient approach to complex polycycles in terms of both selectivity and atom economy.
• Cyclization via isomerization: a palladium(2+)-catalyzed carbocyclization of 1,6-enynes to 1,3- and 1,4-dienes
  作者：Barry M. Trost、Mark Lautens

  DOI：10.1021/ja00292a065

  日期：1985.3