1-Ethynylspiro[3.5]nonan-1-ol | 152568-23-5

• 分子结构分类: 有机化合物 - 有机氧化合物
• 英文名称: 1-Ethynylspiro[3.5]nonan-1-ol
• 英文别名: 3-ethynylspiro[3.5]nonan-3-ol
• CAS: 152568-23-5
• 化学式: C₁₁H₁₆O
• 分子量: 164.247
• InChiKey: RPAQCWJTOFADJL-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  2.2
• 重原子数：
  12
• 可旋转键数：
  1
• 环数：
  2.0
• sp3杂化的碳原子比例：
  0.82
• 拓扑面积：
  20.2
• 氢给体数：
  1
• 氢受体数：
  1

反应信息

• 作为反应物：
  描述：

  1-Ethynylspiro[3.5]nonan-1-ol 在 manganese triacetate 作用下， 以 乙醇 为溶剂， 反应 12.0h， 以45%的产率得到1-Methylenspiro<4.5>decan-2-on
  参考文献：
  名称：

  Manganese(III)-based oxidative fragmentation-cyclization reactions of unsaturated cyclobutanols

  摘要：

  Allylic cyclobutanols 1, 10, 21, 27, 32, 39, 51, and 58 are oxidatively fragmented by Mn(OAc)3.2H2O in EtOH to give tertiary radicals as shown in eq 1. These tertiary radicals undergo both 6-endocyclization to the alpha,beta--unsaturated ketone to afford a-keto radicals and 5-exo-cyclization to provide beta-keto cyclopentylmethyl radicals. The a-keto radicals produced by 6-endo-cyclization are reduced to ketones or dimerize. The beta-keto radicals formed by 5-exo-cyclization are oxidized by Cu(OAc)2 to yield methylenecyclopentanones and rearrange to give 3-oxocyclohexyl radicals that are oxidized by Cu(OAC)2 to afford cyclohexenones. Acetylenic cyclobutanols 47, 49, and 65 are oxidatively fragmented by Mn(OAC)3.2H2O in EtOH to provide tertiary radicals that cyclize to give alpha-keto vinyl radicals, which abstract a hydrogen atom to yield methylenecyclopentanones. Pentenylcyclobutanol 75 is oxidatively fragmented by Mn(OAc)3.2H2O to afford tertiary radical 74, which cyclizes to furnish cyclopentylmethyl radicals 77 and 78, which are oxidized by Cu(OAC)2 to methylenecyclopentanes 76 and 79.

  DOI：

  10.1021/jo00077a054
• 作为产物：
  描述：

  螺[3.5]壬烷-3-酮 、 乙炔锂乙二胺配合物 以 四氢呋喃 为溶剂， 反应 1.0h， 以53%的产率得到1-Ethynylspiro[3.5]nonan-1-ol
  参考文献：
  名称：

  Manganese(III)-based oxidative fragmentation-cyclization reactions of unsaturated cyclobutanols

  摘要：

  Allylic cyclobutanols 1, 10, 21, 27, 32, 39, 51, and 58 are oxidatively fragmented by Mn(OAc)3.2H2O in EtOH to give tertiary radicals as shown in eq 1. These tertiary radicals undergo both 6-endocyclization to the alpha,beta--unsaturated ketone to afford a-keto radicals and 5-exo-cyclization to provide beta-keto cyclopentylmethyl radicals. The a-keto radicals produced by 6-endo-cyclization are reduced to ketones or dimerize. The beta-keto radicals formed by 5-exo-cyclization are oxidized by Cu(OAc)2 to yield methylenecyclopentanones and rearrange to give 3-oxocyclohexyl radicals that are oxidized by Cu(OAC)2 to afford cyclohexenones. Acetylenic cyclobutanols 47, 49, and 65 are oxidatively fragmented by Mn(OAC)3.2H2O in EtOH to provide tertiary radicals that cyclize to give alpha-keto vinyl radicals, which abstract a hydrogen atom to yield methylenecyclopentanones. Pentenylcyclobutanol 75 is oxidatively fragmented by Mn(OAc)3.2H2O to afford tertiary radical 74, which cyclizes to furnish cyclopentylmethyl radicals 77 and 78, which are oxidized by Cu(OAC)2 to methylenecyclopentanes 76 and 79.

  DOI：

  10.1021/jo00077a054

文献信息

• Ruthenium-Catalyzed Ring Expansion Reaction of 1-Acetylenylcyclobutanols with Methyl Vinyl Ketone
  作者：Kenji Sugimoto、Masataka Ihara、Masahiro Yoshida

  DOI：10.1055/s-2006-947346

  日期：2006.8

  ruthenium-catalyzed cascade ring expansion reaction is reported. A 1,2-rearrangement of acetylenylcyclobutanol followed by carbon-carbon bond formation with methyl vinyl ketone proceeds in one-pot process. This reaction enables to synthesize 2-alkylidenecyclopentanones in a stereoselective manner using appropriate ruthenium catalysts.

  报道了一种新型的钌催化级联扩环反应。乙炔基环丁醇的 1,2-重排，随后与甲基乙烯基酮形成碳-碳键，以一锅法进行。该反应能够使用合适的钌催化剂以立体选择性方式合成 2-亚烷基环戊酮。