diethyl (5,5-dicyano-2-pentyl)malonate | 390746-05-1

• 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: diethyl (5,5-dicyano-2-pentyl)malonate
• 英文别名: Diethyl 2-(5,5-dicyanopentan-2-yl)propanedioate
• CAS: 390746-05-1
• 化学式: C₁₄H₂₀N₂O₄
• 分子量: 280.324
• InChiKey: VLHQYZZERJBYSI-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  2.3
• 重原子数：
  20
• 可旋转键数：
  10
• 环数：
  0.0
• sp3杂化的碳原子比例：
  0.71
• 拓扑面积：
  100
• 氢给体数：
  0
• 氢受体数：
  6

反应信息

• 作为反应物：
  描述：

  diethyl (5,5-dicyano-2-pentyl)malonate 在 盐酸 、 potassium fluoride 、 乙醇 、 sodium 作用下， 以 叔丁醇 为溶剂， 反应 41.0h， 生成 (+/-)-diethyl (1R,3RS,6S)-6-cyano-9-ethoxy-3-methylbicyclo[4.4.0]dec-8-en-7-one-2,2-dicarboxylate
  参考文献：
  名称：

  Short Total Syntheses of Both the Putative and Actual Structures of the Clerodane Diterpenoid (±)-Sacacarin by Double Annulation

  摘要：

  [GRAPHICS]The putative structure of the naturally occurring clerodane, diterpenoid (+/-)-sacacarin has been prepared in only 10 steps, six of which are C-C bond-forming steps, in a chemo-, regio-, and diastereoselective manner. The key part of the synthesis is the double annulation (double Michael, Pinner, and Dieckmann reaction) of a tethered carbon diacid and 3-butyn-2-one. A corrected structure for sacacarin is proposed, and the structure is proven by synthesis.

  DOI：

  10.1021/ol016748j
• 作为产物：
  描述：

  diethyl 5,5-dicyano-6-ethyl-2-methyl-6-octene-1,1-dicarboxylate 在 臭氧 、 对甲苯磺酸 作用下， 以 二氯甲烷 、 乙醇 为溶剂， 以88%的产率得到diethyl (5,5-dicyano-2-pentyl)malonate
  参考文献：
  名称：

  Short Total Syntheses of Both the Putative and Actual Structures of the Clerodane Diterpenoid (±)-Sacacarin by Double Annulation

  摘要：

  [GRAPHICS]The putative structure of the naturally occurring clerodane, diterpenoid (+/-)-sacacarin has been prepared in only 10 steps, six of which are C-C bond-forming steps, in a chemo-, regio-, and diastereoselective manner. The key part of the synthesis is the double annulation (double Michael, Pinner, and Dieckmann reaction) of a tethered carbon diacid and 3-butyn-2-one. A corrected structure for sacacarin is proposed, and the structure is proven by synthesis.

  DOI：

  10.1021/ol016748j

文献信息

• Trimethylsilylethynyl Ketones as Surrogates for Ethynyl Ketones in the Double Michael Reaction
  作者：Derrick S. Holeman、Ravindra M. Rasne、Robert B. Grossman

  DOI：10.1021/jo0163086

  日期：2002.5.1

  Trimethylsilylethynyl ketones can be desilylated in the presence of a tethered carbon diacid and induced to undergo a double Michael reaction in situ. The trimethylsilylethynyl ketones can serve as surrogates of ethynyl ketones that are difficult to prepare or isolate.

  三甲基甲硅烷基乙炔基酮可在连接的碳酸二酸存在下被甲硅烷基化，并使其原位发生双重迈克尔反应。三甲基甲硅烷基乙炔基酮可以用作难以制备或分离的乙炔基酮的替代物。