tert-Butyl 5-methylhept-cis-4-en-6-ynoate | 171012-32-1

• 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: tert-Butyl 5-methylhept-cis-4-en-6-ynoate
• 英文别名: tert-butyl (Z)-5-methylhept-4-en-6-ynoate
• CAS: 171012-32-1
• 化学式: C₁₂H₁₈O₂
• 分子量: 194.274
• InChiKey: LRISMBRAJNPMNQ-NTMALXAHSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  2.9
• 重原子数：
  14
• 可旋转键数：
  6
• 环数：
  0.0
• sp3杂化的碳原子比例：
  0.58
• 拓扑面积：
  26.3
• 氢给体数：
  0
• 氢受体数：
  2

反应信息

• 作为反应物：
  描述：

  tert-Butyl 5-methylhept-cis-4-en-6-ynoate 在 咪唑 、 lithium aluminium tetrahydride 、 正丁基锂 、 lithium bromide 作用下， 以 四氢呋喃 、 乙醚 、 正己烷 、 N,N-二甲基甲酰胺 为溶剂， 反应 31.25h， 生成 1-((1E,3Z)-7-Hydroxy-3-methyl-hepta-1,3-dienyl)-2,2,4-trimethyl-3-[2-(2-trimethylsilanyl-ethoxymethoxy)-ethyl]-cyclohex-3-enol
  参考文献：
  名称：

  Taxol Total Synthesis: Preparation of a Chiral Ring A Moiety via Biomimetic Cyclization and Evaluation of a Tandem Nitrile Oxide Strategy for Rings B/C

  摘要：

  A fully functionalized taxol ring A moiety 7 was efficiently prepared via biomimetic cation-olefin cyclization of chiral geraniol epoxide 2b using SnCl4 in toluene. Fractional crystallization provided endo-3 (50% yield from 2b) that was converted to aldehyde 5 by stereospecific epoxidation, secondary alcohol protection, and PCC oxidation. NaOMe-mediated ring opening secured enal 6. Addition of lithium dithiane to 6 at low temperature provided 7 as the sole product in good yield. A tandem nitrile oxide cycloaddition strategy for creating the remaining B/C carbocycles as well as key functionality present in both rings was validated, in part, by cyclization of 14 to tricyclic isoxazoline 15.

  DOI：

  10.1021/jo00127a028
• 作为产物：
  描述：

  (Z)-3-甲基戊-2-烯-4-炔-1-醇 在 N-溴代丁二酰亚胺(NBS) 、 三苯基膦 、 lithium diisopropyl amide 作用下， 以 四氢呋喃 、 正己烷 、 二氯甲烷 为溶剂， 反应 18.5h， 生成 tert-Butyl 5-methylhept-cis-4-en-6-ynoate
  参考文献：
  名称：

  Taxol Total Synthesis: Preparation of a Chiral Ring A Moiety via Biomimetic Cyclization and Evaluation of a Tandem Nitrile Oxide Strategy for Rings B/C

  摘要：

  A fully functionalized taxol ring A moiety 7 was efficiently prepared via biomimetic cation-olefin cyclization of chiral geraniol epoxide 2b using SnCl4 in toluene. Fractional crystallization provided endo-3 (50% yield from 2b) that was converted to aldehyde 5 by stereospecific epoxidation, secondary alcohol protection, and PCC oxidation. NaOMe-mediated ring opening secured enal 6. Addition of lithium dithiane to 6 at low temperature provided 7 as the sole product in good yield. A tandem nitrile oxide cycloaddition strategy for creating the remaining B/C carbocycles as well as key functionality present in both rings was validated, in part, by cyclization of 14 to tricyclic isoxazoline 15.

  DOI：

  10.1021/jo00127a028