dimethyl 3,3-diacetylglutarate | 31862-39-2

• 分子结构分类: 有机化合物 - 有机酸及其衍生物 - 酮酸及其衍生物
• 英文名称: dimethyl 3,3-diacetylglutarate
• 英文别名: Dimethyl-3,3-diacetylglutarat；Dimethyl 3,3-diacetylpentanedioate
• CAS: 31862-39-2
• 化学式: C₁₁H₁₆O₆
• 分子量: 244.244
• InChiKey: JSAWBBQOXIZJNI-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  -0.7
• 重原子数：
  17
• 可旋转键数：
  8
• 环数：
  0.0
• sp3杂化的碳原子比例：
  0.64
• 拓扑面积：
  86.7
• 氢给体数：
  0
• 氢受体数：
  6

反应信息

• 作为反应物：
  描述：

  dimethyl 3,3-diacetylglutarate 、 alkaline earth salt of/the/ methylsulfuric acid 在 [Rh(S)-BINAP]ClO₄ 吡啶 、 4-二甲氨基吡啶 、 lithium aluminium tetrahydride 、 sodium acetate 、 四氯化钛 、 对甲苯磺酸 、 pyridinium chlorochromate 作用下， 以 四氢呋喃 、 乙醚 、 二氯甲烷 、 苯 为溶剂， 反应 14.75h， 生成 (3R,4R)-3-(2-acetoxyethyl)-3-isopropenyl-4-methylcyclopentanone (R,R)-2,3-butanediol acetal
  参考文献：
  名称：

  Enantio- and diastereoselective construction of 4,9-dimethylspiro[4.4]nonane-2,7-dione using Rh-catalyzed asymmetric cyclization

  摘要：

  Asymmetric cyclization using Rh-complexes was applied to the synthesis of 4,9-dimethylspiro[4.4]nonane-2,7-diones. The spiro[4.4]nonane skeleton bearing a chiral quaternary carbon could be stepwisely constructed by using Rh-catalyzed cyclization twice. All diastereomers of the spirodiketone could be stereoselectively prepared from the identical starting material by the combination of a neutral Rh(PPh3)(3)Cl and a cationic Rh[BINAP]ClO4. The cyclization by the neutral Rh(PPh3)(3)Cl proceeded to give cis-3,4-disubstituted cyclopentanones, while that by the cationic Rh[BINAP]ClO4 proceeded to afford trans-3,4-disubstituted cyclopentanones. Four spirodiketones of six stereoisomers could be prepared in optically active form, and the relationship between the stereochemistry of the spirodiketones and the Rh-complex was discussed based on the plausible acyl-hydride Rh-complexes. (C) 2001 Elsevier Science Ltd. All rights reserved.

  DOI：

  10.1016/s0040-4020(00)01106-6
• 作为产物：
  描述：

  溴乙酸甲酯 、 乙酰丙酮 在 potassium carbonate 作用下， 生成 dimethyl 3,3-diacetylglutarate
  参考文献：
  名称：

  吡咯和相关化合物。第十六部分。通过原卟啉-IX的合成一个和- b -oxobilane路由

  摘要：

  2-乙基-2- devinylprotoporphyrin-IX二甲酯已经由合成一个-oxobilane途径，4-乙烯基正由一个新的方法，介绍了即 中间体吡咯之一中存在的β-乙酰氧基乙基侧链的转化。原卟啉-IX二甲酯也已制备两个一-和b -oxobilane路线，再次用β乙酰氧基乙基的基团在卟啉的两个乙烯基的前体。在使用五氯苯基酯pyrromethane的一个-oxobilane合成和在叔丁基酯pyrromethane的b-氧杂环戊烷路线使这些合成反应能够以完全合理的方式进行，而无需涉及对称的中间体，这是因为五氯苯基酯核可以通过温和的碱性水解选择性裂解，而核叔丁基酯则可以在存在苄基的情况下通过三氟乙酸裂解酯。形成在中间oxophlorin b -oxobilane路线经历在用氚交换内消旋的氧代基团-位相反，因此，氧代功能来促进δ-合成内消旋叶绿素领域中进行生物合成实验所需的-化原卟啉-IX

  DOI：

  10.1039/j39710000487

文献信息

• Application of Rh-catalyzed cyclization for the construction of three consecutive chiral carbons in 4,9-dimethylspiro[4.4]nonane-2,7-dione
  作者：Miyuki Takahashi、Masakazu Tanaka*、Eishi Sakamoto、Masanori Imai、Akiko Matsui、Kazuhisa Funakoshi、Kiyoshi Sakai、Hiroshi Suemune

  DOI：10.1016/s0040-4039(00)01315-0

  日期：2000.10

  Asymmetric cyclization using Rh-complexes has been applied to the synthesis of 4,9-dimethylspiro[4.4]nonane-2,7-diones. The spiro[4.4]nonane skeleton bearing three consecutive chiral carbons could be stepwisely constructed from an identical starting material by the combination of a cationic Rh[(S)BINAP]ClO4 and a neutral RhCl(PPh3)(3). The relationship between the stereochemistry of the spirodiketones and the Rh-complex was also discussed. (C) 2000 Elsevier Science Ltd. All rights reserved.
• Pyrroles and related compounds. Part XVI. Synthesis of protoporphyrin-IX by the a- and b-oxobilane routes
  作者：R. P. Carr、A. H. Jackson、G. W. Kenner、G. S. Sach

  DOI：10.1039/j39710000487

  日期：——

  2-Ethyl-2-devinylprotoporphyrin-IX dimethyl ester has been synthesised by the a-oxobilane route, the 4-vinyl group being introduced by a new method, viz. transformation of a β-acetoxyethyl side-chain present in one of the intermediate pyrroles. Protoporphyrin-IX dimethyl ester has also been prepared by both the a- and b-oxobilane routes, again with β-acetoxyethyl groups as precursors of the two vinyl groups in the porphyrin

  2-乙基-2- devinylprotoporphyrin-IX二甲酯已经由合成一个-oxobilane途径，4-乙烯基正由一个新的方法，介绍了即 中间体吡咯之一中存在的β-乙酰氧基乙基侧链的转化。原卟啉-IX二甲酯也已制备两个一-和b -oxobilane路线，再次用β乙酰氧基乙基的基团在卟啉的两个乙烯基的前体。在使用五氯苯基酯pyrromethane的一个-oxobilane合成和在叔丁基酯pyrromethane的b-氧杂环戊烷路线使这些合成反应能够以完全合理的方式进行，而无需涉及对称的中间体，这是因为五氯苯基酯核可以通过温和的碱性水解选择性裂解，而核叔丁基酯则可以在存在苄基的情况下通过三氟乙酸裂解酯。形成在中间oxophlorin b -oxobilane路线经历在用氚交换内消旋的氧代基团-位相反，因此，氧代功能来促进δ-合成内消旋叶绿素领域中进行生物合成实验所需的-化原卟啉-IX
• Enantio- and diastereoselective construction of 4,9-dimethylspiro[4.4]nonane-2,7-dione using Rh-catalyzed asymmetric cyclization
  作者：Masakazu Tanaka、Miyuki Takahashi、Eishi Sakamoto、Masanori Imai、Akiko Matsui、Masakazu Fujio、Kazuhisa Funakoshi、Kiyoshi Sakai、Hiroshi Suemune

  DOI：10.1016/s0040-4020(00)01106-6

  日期：2001.2

  Asymmetric cyclization using Rh-complexes was applied to the synthesis of 4,9-dimethylspiro[4.4]nonane-2,7-diones. The spiro[4.4]nonane skeleton bearing a chiral quaternary carbon could be stepwisely constructed by using Rh-catalyzed cyclization twice. All diastereomers of the spirodiketone could be stereoselectively prepared from the identical starting material by the combination of a neutral Rh(PPh3)(3)Cl and a cationic Rh[BINAP]ClO4. The cyclization by the neutral Rh(PPh3)(3)Cl proceeded to give cis-3,4-disubstituted cyclopentanones, while that by the cationic Rh[BINAP]ClO4 proceeded to afford trans-3,4-disubstituted cyclopentanones. Four spirodiketones of six stereoisomers could be prepared in optically active form, and the relationship between the stereochemistry of the spirodiketones and the Rh-complex was discussed based on the plausible acyl-hydride Rh-complexes. (C) 2001 Elsevier Science Ltd. All rights reserved.