methyl 4-(5,9,9-trimethyl-6,7,8,9-tetrahydronaphtho[1,2-d][1,3]dioxol-4-yl)-2-butynoate | 1189021-15-5

• 分子结构分类: 有机化合物 - 有机杂环化合物
• 英文名称: methyl 4-(5,9,9-trimethyl-6,7,8,9-tetrahydronaphtho[1,2-d][1,3]dioxol-4-yl)-2-butynoate
• 英文别名: methyl 4-(5,9,9-trimethyl-7,8-dihydro-6H-benzo[g][1,3]benzodioxol-4-yl)but-2-ynoate
• CAS: 1189021-15-5
• 化学式: C₁₉H₂₂O₄
• 分子量: 314.381
• InChiKey: DXLNLPOXEBTJHW-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  5.1
• 重原子数：
  23
• 可旋转键数：
  2
• 环数：
  3.0
• sp3杂化的碳原子比例：
  0.53
• 拓扑面积：
  44.8
• 氢给体数：
  0
• 氢受体数：
  4

反应信息

• 作为反应物：
  描述：

  methyl 4-(5,9,9-trimethyl-6,7,8,9-tetrahydronaphtho[1,2-d][1,3]dioxol-4-yl)-2-butynoate 、 甲基锂 在 copper(l) iodide 、 氯化铵 作用下， 以 四氢呋喃 、 乙醚 、 水 为溶剂， 反应 2.25h， 以95%的产率得到(Z)-methyl 3-methyl-4-(5,9,9-trimethyl-6,7,8,9-tetrahydronaphtho[1,2-d][1,3]dioxol-4-yl)-2-butenoate
  参考文献：
  名称：

  The Synthesis of Velloziolide via Nicholas Reaction Based γ-Carbonyl Cations

  摘要：

  The total synthesis of the 9,11-seco-rosane diterpene velloziolide (1) has been accomplished by employing the Nicholas reaction chemistry of 2a as a gamma-carbonyl cation equivalent. An initial model Study demonstrated the utility of Nicholas reactions of 2 in the generation of 4-arylalkynoate Co(2)(CO)(6) complexes, and in conjunction with Gilman cuprate addition and Johnson-Claisen rearrangement chemistry, the preparation of a 3-methyl-3-vinyl-4-arylalkanoate model for velloziolide. The Nicholas reaction/gamma-carbonyl cation methodology was then employed twice in the total synthesis to incorporate onto 3,4-methylenedioxytoluene the 4-carbon unit that became the gem-dimethyltetralin portion of the velloziolide and, subsequently, to incorporate the gamma-arylalkanoate function of the epsilon-lactone.

  DOI：

  10.1021/jo901471b
• 作为产物：
  描述：

  5,9,9-trimethyl-6,7,8,9-tetrahydronaphtho[1,2-d][1,3]dioxole 、 alkaline earth salt of/the/ methylsulfuric acid 在 三氟甲磺酸二丁硼 、 氯化铵 、 碘 作用下， 以 二氯甲烷 、 水 、 四氢呋喃 为溶剂， 反应 13.0h， 以92%的产率得到methyl 4-(5,9,9-trimethyl-6,7,8,9-tetrahydronaphtho[1,2-d][1,3]dioxol-4-yl)-2-butynoate
  参考文献：
  名称：

  The Synthesis of Velloziolide via Nicholas Reaction Based γ-Carbonyl Cations

  摘要：

  The total synthesis of the 9,11-seco-rosane diterpene velloziolide (1) has been accomplished by employing the Nicholas reaction chemistry of 2a as a gamma-carbonyl cation equivalent. An initial model Study demonstrated the utility of Nicholas reactions of 2 in the generation of 4-arylalkynoate Co(2)(CO)(6) complexes, and in conjunction with Gilman cuprate addition and Johnson-Claisen rearrangement chemistry, the preparation of a 3-methyl-3-vinyl-4-arylalkanoate model for velloziolide. The Nicholas reaction/gamma-carbonyl cation methodology was then employed twice in the total synthesis to incorporate onto 3,4-methylenedioxytoluene the 4-carbon unit that became the gem-dimethyltetralin portion of the velloziolide and, subsequently, to incorporate the gamma-arylalkanoate function of the epsilon-lactone.

  DOI：

  10.1021/jo901471b