(2R,2'R,4'aR,5R,8'aR)-decahydro-2'-hydroxy-2',5,5',5',8'a-pentamethylspiro(furan-2(3H),1'(2'H)-naphthalene)-5-acetaldehyde | 180628-06-2

• 分子结构分类: 有机化合物 - 脂质和类脂质分子 - 异戊烯醇脂质
• 英文名称: (2R,2'R,4'aR,5R,8'aR)-decahydro-2'-hydroxy-2',5,5',5',8'a-pentamethylspiro(furan-2(3H),1'(2'H)-naphthalene)-5-acetaldehyde
• CAS: 180628-06-2
• 化学式: C₂₀H₃₄O₃
• 分子量: 322.488
• InChiKey: HMXNMUBYICTKPW-YHUYVZNPSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  4.26
• 重原子数：
  23.0
• 可旋转键数：
  2.0
• 环数：
  3.0
• sp3杂化的碳原子比例：
  0.95
• 拓扑面积：
  46.53
• 氢给体数：
  1.0
• 氢受体数：
  3.0

反应信息

• 作为反应物：
  描述：

  (2R,2'R,4'aR,5R,8'aR)-decahydro-2'-hydroxy-2',5,5',5',8'a-pentamethylspiro(furan-2(3H),1'(2'H)-naphthalene)-5-acetaldehyde 在 吡啶 、 4-二甲氨基吡啶 、 氢氧化钾 、 氯化亚砜 、 碘 作用下， 反应 0.5h， 生成 methyl (2S,4'aR,5R,8'aR)-decahydro-5,5',5',8'a-tetramethylspiro-5-acetate
  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：

  (2R,2'R,4'aR,5R,8'aR)-decahydro-2',5,5',5',8'a-pentamethyl-5-vinylspiro-2'-ol 在 sodium hydroxide 、 4 A molecular sieve 、 双氧水 、 pyridinium chlorochromate 、 diborane(6) 作用下， 以 二氯甲烷 为溶剂， 反应 19.5h， 生成 (2R,2'R,4'aR,5R,8'aR)-decahydro-2'-hydroxy-2',5,5',5',8'a-pentamethylspiro(furan-2(3H),1'(2'H)-naphthalene)-5-acetaldehyde
  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