(2S)-1,2-epoxy-6-(trimethylsilyl)-4-hexyne | 145987-95-7

• 分子结构分类: 有机化合物 - 有机杂环化合物 - 环氧化物
• 英文名称: (2S)-1,2-epoxy-6-(trimethylsilyl)-4-hexyne
• 英文别名: trimethyl-[4-[(2S)-oxiran-2-yl]but-2-ynyl]silane
• CAS: 145987-95-7
• 化学式: C₉H₁₆OSi
• 分子量: 168.311
• InChiKey: AKXWBBHRODOHOB-VIFPVBQESA-N

计算性质

• 辛醇/水分配系数(LogP)：
  2.12
• 重原子数：
  11
• 可旋转键数：
  2
• 环数：
  1.0
• sp3杂化的碳原子比例：
  0.78
• 拓扑面积：
  12.5
• 氢给体数：
  0
• 氢受体数：
  1

反应信息

• 作为反应物：
  描述：

  (2S)-1,2-epoxy-6-(trimethylsilyl)-4-hexyne 在 Lindlar's catalyst 四丁基氟化铵 、 氢气 、 六甲基二硅氮烷 、 pyridinium chlorochromate 作用下， 以 正己烷 为溶剂， 生成 (1S,2R)-2-ethenylcyclopropane-1-carbaldehyde
  参考文献：
  名称：

  Synthesis of vinylcyclopropanes by intramolecular epoxide ring opening. Application for an enantioselective synthesis of dictyopterene A

  摘要：

  The reaction of functionalized oxiranes 1 with the sulfur- or silicon-stabilized anions 2 provides beta-heteroatom-substituted gamma,delta-unsaturated epoxides 5 with, for 5e,f, a trans C=C moiety. A cis compound 9 is obtained using acetylide anion 2c via 7 and subsequent partial hydrogenation of the C=C bond in the intermediate oxirane 8. Regiospecific anion generation in 5,9 is achieved by deprotonation, reductive desulfurization, and desilylation, respectively. The resulting anions 10 cyclize to 1-(hydroxyalkyl)-2-vinylcyclopropanes 11 by a stereochemically controlled S(N)i Process. Starting from the optically active epoxide 1b, the approach allows synthesis of cyclopropane 11b with (1S,2R) configuration at the ring carbon atoms. This compound can be further elaborated to the algae sex pheromone dictyopterene A which is obtained along with the unnatural Z diastereomer.

  DOI：

  10.1021/jo00055a014
• 作为产物：
  描述：

  炔丙基三甲基硅烷 在 正丁基锂 、 三氟化硼乙醚 、 potassium carbonate 作用下， 以 甲醇 为溶剂， 反应 2.17h， 生成 (2S)-1,2-epoxy-6-(trimethylsilyl)-4-hexyne
  参考文献：
  名称：

  Synthesis of vinylcyclopropanes by intramolecular epoxide ring opening. Application for an enantioselective synthesis of dictyopterene A

  摘要：

  The reaction of functionalized oxiranes 1 with the sulfur- or silicon-stabilized anions 2 provides beta-heteroatom-substituted gamma,delta-unsaturated epoxides 5 with, for 5e,f, a trans C=C moiety. A cis compound 9 is obtained using acetylide anion 2c via 7 and subsequent partial hydrogenation of the C=C bond in the intermediate oxirane 8. Regiospecific anion generation in 5,9 is achieved by deprotonation, reductive desulfurization, and desilylation, respectively. The resulting anions 10 cyclize to 1-(hydroxyalkyl)-2-vinylcyclopropanes 11 by a stereochemically controlled S(N)i Process. Starting from the optically active epoxide 1b, the approach allows synthesis of cyclopropane 11b with (1S,2R) configuration at the ring carbon atoms. This compound can be further elaborated to the algae sex pheromone dictyopterene A which is obtained along with the unnatural Z diastereomer.

  DOI：

  10.1021/jo00055a014

文献信息

• Synthesis of vinylcyclopropanes by intramolecular epoxide ring opening. Application for an enantioselective synthesis of dictyopterene A
  作者：Frank Narjes、Oliver Bolte、Detlef Icheln、Wilfried A. Koenig、Ernst Schaumann

  DOI：10.1021/jo00055a014

  日期：1993.1

  The reaction of functionalized oxiranes 1 with the sulfur- or silicon-stabilized anions 2 provides beta-heteroatom-substituted gamma,delta-unsaturated epoxides 5 with, for 5e,f, a trans C=C moiety. A cis compound 9 is obtained using acetylide anion 2c via 7 and subsequent partial hydrogenation of the C=C bond in the intermediate oxirane 8. Regiospecific anion generation in 5,9 is achieved by deprotonation, reductive desulfurization, and desilylation, respectively. The resulting anions 10 cyclize to 1-(hydroxyalkyl)-2-vinylcyclopropanes 11 by a stereochemically controlled S(N)i Process. Starting from the optically active epoxide 1b, the approach allows synthesis of cyclopropane 11b with (1S,2R) configuration at the ring carbon atoms. This compound can be further elaborated to the algae sex pheromone dictyopterene A which is obtained along with the unnatural Z diastereomer.