({[(2E)-4-(Methoxymethoxy)-3-methyl-2-butenyl]oxy}methyl)benzene | 900149-80-6

• 分子结构分类: 有机化合物 - 苯类化合物 - 苯和取代衍生物
• 英文名称: ({[(2E)-4-(Methoxymethoxy)-3-methyl-2-butenyl]oxy}methyl)benzene
• 英文别名: [(E)-4-(methoxymethoxy)-3-methylbut-2-enoxy]methylbenzene
• CAS: 900149-80-6
• 化学式: C₁₄H₂₀O₃
• 分子量: 236.311
• InChiKey: PJNIJQSPHBMVHQ-MDWZMJQESA-N

计算性质

• 辛醇/水分配系数(LogP)：
  2.3
• 重原子数：
  17
• 可旋转键数：
  8
• 环数：
  1.0
• sp3杂化的碳原子比例：
  0.43
• 拓扑面积：
  27.7
• 氢给体数：
  0
• 氢受体数：
  3

反应信息

• 作为反应物：
  描述：

  ({[(2E)-4-(Methoxymethoxy)-3-methyl-2-butenyl]oxy}methyl)benzene 在 palladium on activated charcoal 、 (DHQ)2-PHAL 、 potassium hexacyanoferrate(III) potassium osmate(VI) 、 AD-mix-α 、 甲基磺酰胺 、 氢气 、 sodium hydride 作用下， 以 四氢呋喃 、 甲醇 、 水 、 叔丁醇 为溶剂， 反应 82.0h， 生成
  参考文献：
  名称：

  Exploration of conjugate addition routes to advanced tricyclic components of mangicol A

  摘要：

  Two synthetic approaches to the cytotoxic marine natural product known as mangicol A are described. The starting material common to both pathways is the cyclopentenonecarboxylate 11. The first tactic involves the 1,4-addition to 11 of the cuprate derivable from iodide 10, while the second proceeds via base-promoted conjugate addition of the regiospecifically generated enolate anion of 41. The first strategy proceeds by a series of efficient steps to tricyclic aldol 21 and subsequently to beta-diketone 7. The latter proved to be totally unresponsive to schemes aimed at introduction of a butenyl group. The second approach involves earlier introduction of this substituent as realized in stereo-controlled fashion via transition state 42. While further passage to 44 proved uneventful, this advanced intermediate and analogs thereof proved remarkably recalcitrant to cyclization in the precedented fashion. In no instance was generation of a suitable product realized. These studies serve to underscore the extent to which steric considerations can complicate matters and the extent to which they must be skirted. Finally, a direct enantioselective route to the side chain aldehyde 2 is detailed. (c) 2006 Elsevier Ltd. All rights reserved.

  DOI：

  10.1016/j.tet.2006.03.066
• 作为产物：
  描述：

  梨醇酯 在 叔丁基过氧化氢 、 lithium hydroxide 、 selenium(IV) oxide 、 四丁基碘化铵 、 sodium hydride 、 大茴香酸 、 N,N-二异丙基乙胺 作用下， 以 四氢呋喃 、 水 为溶剂， 反应 41.0h， 生成 ({[(2E)-4-(Methoxymethoxy)-3-methyl-2-butenyl]oxy}methyl)benzene
  参考文献：
  名称：

  Exploration of conjugate addition routes to advanced tricyclic components of mangicol A

  摘要：

  Two synthetic approaches to the cytotoxic marine natural product known as mangicol A are described. The starting material common to both pathways is the cyclopentenonecarboxylate 11. The first tactic involves the 1,4-addition to 11 of the cuprate derivable from iodide 10, while the second proceeds via base-promoted conjugate addition of the regiospecifically generated enolate anion of 41. The first strategy proceeds by a series of efficient steps to tricyclic aldol 21 and subsequently to beta-diketone 7. The latter proved to be totally unresponsive to schemes aimed at introduction of a butenyl group. The second approach involves earlier introduction of this substituent as realized in stereo-controlled fashion via transition state 42. While further passage to 44 proved uneventful, this advanced intermediate and analogs thereof proved remarkably recalcitrant to cyclization in the precedented fashion. In no instance was generation of a suitable product realized. These studies serve to underscore the extent to which steric considerations can complicate matters and the extent to which they must be skirted. Finally, a direct enantioselective route to the side chain aldehyde 2 is detailed. (c) 2006 Elsevier Ltd. All rights reserved.

  DOI：

  10.1016/j.tet.2006.03.066

文献信息

• Exploration of conjugate addition routes to advanced tricyclic components of mangicol A
  作者：Stefan Pichlmair、Manuel de Lera Ruiz、Ivan Vilotijevic、Leo A. Paquette

  DOI：10.1016/j.tet.2006.03.066

  日期：2006.6

  Two synthetic approaches to the cytotoxic marine natural product known as mangicol A are described. The starting material common to both pathways is the cyclopentenonecarboxylate 11. The first tactic involves the 1,4-addition to 11 of the cuprate derivable from iodide 10, while the second proceeds via base-promoted conjugate addition of the regiospecifically generated enolate anion of 41. The first strategy proceeds by a series of efficient steps to tricyclic aldol 21 and subsequently to beta-diketone 7. The latter proved to be totally unresponsive to schemes aimed at introduction of a butenyl group. The second approach involves earlier introduction of this substituent as realized in stereo-controlled fashion via transition state 42. While further passage to 44 proved uneventful, this advanced intermediate and analogs thereof proved remarkably recalcitrant to cyclization in the precedented fashion. In no instance was generation of a suitable product realized. These studies serve to underscore the extent to which steric considerations can complicate matters and the extent to which they must be skirted. Finally, a direct enantioselective route to the side chain aldehyde 2 is detailed. (c) 2006 Elsevier Ltd. All rights reserved.