(1R,2R)-2-carboxy-2,6,6-trimethylcyclohexanepropionic acid dimethyl ester | 170081-06-8

• 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: (1R,2R)-2-carboxy-2,6,6-trimethylcyclohexanepropionic acid dimethyl ester
• 英文别名: methyl (1R,2R)-2-(3-methoxy-3-oxopropyl)-1,3,3-trimethylcyclohexane-1-carboxylate
• CAS: 170081-06-8
• 化学式: C₁₅H₂₆O₄
• 分子量: 270.369
• InChiKey: CWPUNPKBLKZILT-IAQYHMDHSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  3.3
• 重原子数：
  19
• 可旋转键数：
  6
• 环数：
  1.0
• sp3杂化的碳原子比例：
  0.87
• 拓扑面积：
  52.6
• 氢给体数：
  0
• 氢受体数：
  4

反应信息

• 作为反应物：
  描述：

  (1R,2R)-2-carboxy-2,6,6-trimethylcyclohexanepropionic acid dimethyl ester 在 cerium(III) chloride 、 camphor-10-sulfonic acid 、 sodium hexamethyldisilazane 、 lithium chloride 作用下， 以 四氢呋喃 、 水 、 二甲基亚砜 为溶剂， 反应 4.83h， 生成 (2R,2'R,4'aR,5R,8'aR)-decahydro-2',5,5',5',8'a-pentamethyl-5-vinylspiro-2'-ol
  参考文献：
  名称：

  Stereocontrolled Synthesis of ent-Grindelic Acid. A Useful Example of Diastereofacial Guidance in an Oxonium Ion-Initiated Pinacolic Ring Expansion

  摘要：

  An enantioselective synthesis of (+)-grindelic acid is described, confirming that the dextrorotatory enantiomer is antipodal to the natural diterpenoid. The optically pure bicyclic ketone 5 representing the AB ring system is constructed from the levorotatory Wieland-Miescher ketone and must therefore possess the absolute configuration shown. Coupling of 5 with the 5-lithio derivative of optically active 2,3-dihydrofuran 3 derived from (R)-(-)-linalool was effected for the purpose of realizing acid-catalyzed rearrangement with generation of the appropriate spirocyclic framework. This key step is highly stereocontrolled, leading predominantly to 7. Once the advanced intermediate 15 is available in this fashion, its subsequent exposure to oxidation and dehydration steps led to the target molecule. The synthesis demonstrates unequivocally that natural (-)-grindelic acid is a true labdane diterpenoid.

  DOI：

  10.1021/jo960547p
• 作为产物：
  描述：

  5,5,8aβ-trimethyl-3,4,4aα,5,6,7,8,8a-octahydronaphthalen-1(2H)-one 在 lead(IV) acetate 、 sodium hydroxide 、 sodium chlorite 、 sodium dihydrogenphosphate 、 2-甲基-2-丁烯 、 硫酸 、 pyridinium hydrobromide perbromide 、 溶剂黄146 作用下， 以 水 、 N,N-二甲基甲酰胺 、 叔丁醇 、 苯 为溶剂， 反应 13.5h， 生成 (1R,2R)-2-carboxy-2,6,6-trimethylcyclohexanepropionic acid dimethyl ester
  参考文献：
  名称：

  Stereocontrolled Synthesis of ent-Grindelic Acid. A Useful Example of Diastereofacial Guidance in an Oxonium Ion-Initiated Pinacolic Ring Expansion

  摘要：

  An enantioselective synthesis of (+)-grindelic acid is described, confirming that the dextrorotatory enantiomer is antipodal to the natural diterpenoid. The optically pure bicyclic ketone 5 representing the AB ring system is constructed from the levorotatory Wieland-Miescher ketone and must therefore possess the absolute configuration shown. Coupling of 5 with the 5-lithio derivative of optically active 2,3-dihydrofuran 3 derived from (R)-(-)-linalool was effected for the purpose of realizing acid-catalyzed rearrangement with generation of the appropriate spirocyclic framework. This key step is highly stereocontrolled, leading predominantly to 7. Once the advanced intermediate 15 is available in this fashion, its subsequent exposure to oxidation and dehydration steps led to the target molecule. The synthesis demonstrates unequivocally that natural (-)-grindelic acid is a true labdane diterpenoid.

  DOI：

  10.1021/jo960547p

文献信息

• Total synthesis of (+)-grindelic acid by stereocontrolled oxonium ion activated pinacol ring expansion. Chemical proof of the absolute configuration of all grindelane diterpenes
  作者：Leo A. Paquette、Hui-Ling Wang

  DOI：10.1016/0040-4039(95)01187-m

  日期：1995.8

  (+)-Grindelic acid, synthesized enantioselectively from the levorotatory Wieland-Miescher ketone and (-)-linalool and necessarily formulated as 1a, is shown to be antipodal to the major diterpenoid of Grindelia species.

  (+)-Grindelic酸是由左旋Wieland-Miescher酮和（-)-香叶醇对映选择性合成而得，并必须以1a的形式配制，研究表明其对映于Grindelia属主要的倍半萜。