diethyl 2-[1-(2-furyl)-2,2-dimethyl-3-oxobutyl]malonate

• 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 2-[1-(2-furyl)-2,2-dimethyl-3-oxobutyl]malonate
• 英文别名: Diethyl 2-[1-(furan-2-yl)-2,2-dimethyl-3-oxobutyl]propanedioate
• 化学式: C₁₇H₂₄O₆
• 分子量: 324.374
• InChiKey: GITYDUXZSOMDPH-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  2.3
• 重原子数：
  23
• 可旋转键数：
  10
• 环数：
  1.0
• sp3杂化的碳原子比例：
  0.59
• 拓扑面积：
  82.8
• 氢给体数：
  0
• 氢受体数：
  6

反应信息

• 作为反应物：
  描述：

  diethyl 2-[1-(2-furyl)-2,2-dimethyl-3-oxobutyl]malonate 在 potassium tert-butylate 作用下， 以 四氢呋喃 、 叔丁醇 为溶剂， 反应 1.5h， 以88%的产率得到ethyl [6-(2-furyl)-2-hydroxy-5,5-dimethyl-4-oxo-1-cyclohexene]carboxylate
  参考文献：
  名称：

  Revisiting [3 + 3] Route to 1,3-Cyclohexanedione Frameworks:  Hidden Aspect of Thermodynamically Controlled Enolates

  摘要：

  We have revisited the traditional consecutive Michael-Claisen [3 + 3] process (MC-[3 + 3]) promising the synthesis of a cyclohexane-1,3-dione derivatives from nonactivated simple ketones and enoates and evaluated its potential in modern organic synthesis. Twenty to thirty examples were demonstrated to be effective. The reactions exhibited remarkable regioselectivity with the Michael addition proceeding through nucleophilic attack by the more hindered site of the ketones without exception. The subsequent Claisen condensation resulted in the formation of carbon-carbon bonds between less hindered site of the ketones and acyl carbon of the enoates. The MC-[3 + 3] process described is useful for the synthesis of Taxol A-ring synthons in multigram quantities and for the synthesis of other six-membered carbocyclic compounds. A number of control experiments have been conducted to provide strong support for the mechanism of this MC-[3 + 3].

  DOI：

  10.1021/jo010325d
• 作为产物：
  描述：

  3-甲基-2-丁酮 、 2-(呋喃-2-基亚甲基)丙二酸二乙酯 在 正丁基锂 作用下， 以 四氢呋喃 、 正己烷 、 叔丁醇 为溶剂， 反应 0.08h， 以90%的产率得到diethyl 2-[1-(2-furyl)-2,2-dimethyl-3-oxobutyl]malonate
  参考文献：
  名称：

  Revisiting [3 + 3] Route to 1,3-Cyclohexanedione Frameworks:  Hidden Aspect of Thermodynamically Controlled Enolates

  摘要：

  We have revisited the traditional consecutive Michael-Claisen [3 + 3] process (MC-[3 + 3]) promising the synthesis of a cyclohexane-1,3-dione derivatives from nonactivated simple ketones and enoates and evaluated its potential in modern organic synthesis. Twenty to thirty examples were demonstrated to be effective. The reactions exhibited remarkable regioselectivity with the Michael addition proceeding through nucleophilic attack by the more hindered site of the ketones without exception. The subsequent Claisen condensation resulted in the formation of carbon-carbon bonds between less hindered site of the ketones and acyl carbon of the enoates. The MC-[3 + 3] process described is useful for the synthesis of Taxol A-ring synthons in multigram quantities and for the synthesis of other six-membered carbocyclic compounds. A number of control experiments have been conducted to provide strong support for the mechanism of this MC-[3 + 3].

  DOI：

  10.1021/jo010325d

文献信息

• Revisiting [3 + 3] Route to 1,3-Cyclohexanedione Frameworks:  Hidden Aspect of Thermodynamically Controlled Enolates
  作者：Teruhiko Ishikawa、Ryuichiro Kadoya、Masaki Arai、Haruka Takahashi、Yumi Kaisi、Tomohiro Mizuta、Kazusa Yoshikai、Seiki Saito

  DOI：10.1021/jo010325d

  日期：2001.11.1

  We have revisited the traditional consecutive Michael-Claisen [3 + 3] process (MC-[3 + 3]) promising the synthesis of a cyclohexane-1,3-dione derivatives from nonactivated simple ketones and enoates and evaluated its potential in modern organic synthesis. Twenty to thirty examples were demonstrated to be effective. The reactions exhibited remarkable regioselectivity with the Michael addition proceeding through nucleophilic attack by the more hindered site of the ketones without exception. The subsequent Claisen condensation resulted in the formation of carbon-carbon bonds between less hindered site of the ketones and acyl carbon of the enoates. The MC-[3 + 3] process described is useful for the synthesis of Taxol A-ring synthons in multigram quantities and for the synthesis of other six-membered carbocyclic compounds. A number of control experiments have been conducted to provide strong support for the mechanism of this MC-[3 + 3].