1-(1'-hydroxy-4'-methoxy-2'-butynyl)-1-(3'-propenyl)cyclohexane | 122917-12-8

• 分子结构分类: 有机化合物 - 有机氧化合物
• 英文名称: 1-(1'-hydroxy-4'-methoxy-2'-butynyl)-1-(3'-propenyl)cyclohexane
• 英文别名: 4-Methoxy-1-(1-prop-2-enylcyclohexyl)but-2-yn-1-ol
• CAS: 122917-12-8
• 化学式: C₁₄H₂₂O₂
• 分子量: 222.327
• InChiKey: DXILNGBLUNTVJA-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  2.8
• 重原子数：
  16
• 可旋转键数：
  4
• 环数：
  1.0
• sp3杂化的碳原子比例：
  0.71
• 拓扑面积：
  29.5
• 氢给体数：
  1
• 氢受体数：
  2

反应信息

• 作为反应物：
  描述：

  1-(1'-hydroxy-4'-methoxy-2'-butynyl)-1-(3'-propenyl)cyclohexane 以76%的产率得到
  参考文献：
  名称：

  TROST, BARRY M.;LEE, DONNA C.;RISE, FRODE, TETRAHEDRON LETT., 30,(1989) N, C. 651-654

  摘要：

  DOI：
• 作为产物：
  描述：

  1-allylcyclohexanecarbaldehyde 、 甲基炔丙基醚 在 正丁基锂 作用下， 生成 1-(1'-hydroxy-4'-methoxy-2'-butynyl)-1-(3'-propenyl)cyclohexane
  参考文献：
  名称：

  Pd-Catalyzed Cycloisomerization to 1,2-Dialkylidenecycloalkanes. 2. Alternative Catalyst System

  摘要：

  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.

  DOI：

  10.1021/ja00089a016

文献信息

• A new palladium catalyst for intramolecular carbametalations of enynes
  作者：Barry M. Trost、Donna C. Lee、Frode Rise

  DOI：10.1016/s0040-4039(01)80273-2

  日期：——
• TROST, BARRY M.;LEE, DONNA C.;RISE, FRODE, TETRAHEDRON LETT., 30,(1989) N, C. 651-654
  作者：TROST, BARRY M.、LEE, DONNA C.、RISE, FRODE

  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.