4-acetyl-5-bromo-4-pentenoic acid methyl ester | 484051-81-2

• 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: 4-acetyl-5-bromo-4-pentenoic acid methyl ester
• 英文别名: methyl (4E)-4-(bromomethylidene)-5-oxohexanoate
• CAS: 484051-81-2
• 化学式: C₈H₁₁BrO₃
• 分子量: 235.078
• InChiKey: YGNYJRKXQMADMU-FNORWQNLSA-N

物化性质

• 沸点：
  270.3±40.0 °C(Predicted)
• 密度：
  1.401±0.06 g/cm3(Predicted)

计算性质

• 辛醇/水分配系数(LogP)：
  1
• 重原子数：
  12
• 可旋转键数：
  5
• 环数：
  0.0
• sp3杂化的碳原子比例：
  0.5
• 拓扑面积：
  43.4
• 氢给体数：
  0
• 氢受体数：
  3

反应信息

• 作为反应物：
  描述：

  4-acetyl-5-bromo-4-pentenoic acid methyl ester 在 palladium on activated charcoal tetraphosphorus decasulfide 、 氢气 、 镍 、 对甲苯磺酸 、 三乙胺 作用下， 以 四氢呋喃 、 甲醇 、 水 、 溶剂黄146 、 甲苯 、 xylene 为溶剂， 反应 53.0h， 生成 (+/-)-minovincine
  参考文献：
  名称：

  Synthesis of Vinca Alkaloids and Related Compounds. 90.¹ New Results in the Synthesis of Alkaloids with the Aspidospermane Skeleton. First Total Synthesis of (±)-3-Oxominovincine

  摘要：

  The tryptamine derivative 1 readily reacted with methyl 4-acetyl-5-bromopent-4-enoate (9) that had been built up from 2,4-pentanedione. On intramolecular dehydration and subsequent [4 + 2] cycloaddition, the reaction product 10 gave the epimers 12 and 13 having the D-secoaspidospermane skeleton. Compound 12 directly and 13 after epimerization yielded (+/-)-3-oxominovincine (14). Regioselective reduction of 14 furnished (+)-minovincine (17).

  DOI：

  10.1021/jo9713464
• 作为产物：
  描述：

  4-乙酰基-5-羰基己酸甲酯 在 四丁基氯化铵 、 溴 、 potassium carbonate 作用下， 以 六甲基磷酰三胺 、 二氯甲烷 、 水 为溶剂， 反应 25.0h， 生成 4-acetyl-5-bromo-4-pentenoic acid methyl ester
  参考文献：
  名称：

  Synthesis of Vinca Alkaloids and Related Compounds. 90.¹ New Results in the Synthesis of Alkaloids with the Aspidospermane Skeleton. First Total Synthesis of (±)-3-Oxominovincine

  摘要：

  The tryptamine derivative 1 readily reacted with methyl 4-acetyl-5-bromopent-4-enoate (9) that had been built up from 2,4-pentanedione. On intramolecular dehydration and subsequent [4 + 2] cycloaddition, the reaction product 10 gave the epimers 12 and 13 having the D-secoaspidospermane skeleton. Compound 12 directly and 13 after epimerization yielded (+/-)-3-oxominovincine (14). Regioselective reduction of 14 furnished (+)-minovincine (17).

  DOI：

  10.1021/jo9713464

文献信息

• Sequential Acid/Base-Catalyzed Polycyclization of Tryptamine Derivatives. A Rapid Access to Büchi's Ketone
  作者：Nicolas Heureux、Johan Wouters、István E. Markó

  DOI：10.1021/ol0521127

  日期：2005.11.1

  [reaction: see text] The development of an efficient and diastereoselective methodology that allows the rapid construction of the tetracyclic core of the Aspidosperma and Strychnos alkaloid families is described. Our approach relies upon two key steps: a sequential silica gel/potassium tert-butoxide polycyclization of a tryptamine precursor and a tandem oxidative decarboxylation/ring-closing reaction

  [反应：见正文]本文描述了一种高效且非对映选择性的方法的开发，该方法允许快速构建天冬孢子虫和马兜铃生物碱家族的四环核心。我们的方法依赖于两个关键步骤：色胺的前驱体相继进行硅胶/叔丁醇钾多环化和串联氧化脱羧/闭环反应。使用这种方法可以完成长春步松合成中的关键中间体Buchi酮的组装。
• Synthesis of vinca alkaloids and related compounds. Part 101: A new convergent synthetic pathway to build up the aspidospermane skeleton. Simple synthesis of 3-oxovincadifformine and 3-oxominovincine. Attempts to produce 15β-hydroxyvincadifformine
  作者：János Éles、György Kalaus、István Greiner、Mária Kajtár-Peredy、Pál Szabó、Lajos Szabó、Csaba Szántay

  DOI：10.1016/s0040-4020(02)01179-1

  日期：2002.10

  A molecule with an indole skeleton, containing a latent acrylic ester function—acting as a diene—was produced from Nb-trityl-2-(hydroxy-methyl)-tryptamine and reacted with esters containing an aldehyde or aldehyde-equivalent structural unit, yielding 3-oxo-16,17-dihydro-Δ20-secodin-17-ol type intermediates from which dehydration, followed by [4+2]cycloaddition, furnished 3-oxovincadifformine and 3-oxominovincine

  由N b-三苯甲基-2-（羟基-甲基）-色胺产生具有吲哚骨架的分子，该分子具有潜在的丙烯酸酯功能（起二烯作用），并与含有醛或醛当量结构单元的酯反应，得到3-氧代-16,17-二氢- Δ 20 -secodin -17-醇型中间体从脱水，接着[4 + 2]环加成，陈设3- oxovincadifformine和3- oxominovincine。我们还希望将该方法用于生产15β-羟基长春新碱，但是，观察到具有吲哚骨架的二聚产物的出现，而不是预期的环加成。
• Synthesis of Vinca Alkaloids and Related Compounds. 90.¹ New Results in the Synthesis of Alkaloids with the Aspidospermane Skeleton. First Total Synthesis of (±)-3-Oxominovincine
  作者：György Kalaus、Imre Juhász、István Greiner、Mária Kajtár-Peredy、János Brlik、Lajos Szabó、Csaba Szántay

  DOI：10.1021/jo9713464

  日期：1997.12.1

  The tryptamine derivative 1 readily reacted with methyl 4-acetyl-5-bromopent-4-enoate (9) that had been built up from 2,4-pentanedione. On intramolecular dehydration and subsequent [4 + 2] cycloaddition, the reaction product 10 gave the epimers 12 and 13 having the D-secoaspidospermane skeleton. Compound 12 directly and 13 after epimerization yielded (+/-)-3-oxominovincine (14). Regioselective reduction of 14 furnished (+)-minovincine (17).