methyl grindelate | 170081-10-4

• 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: methyl grindelate
• 英文别名: methyl 2-[(2'R,4aR,8S,8aR)-2',4,4,7,8a-pentamethylspiro[2,3,4a,5-tetrahydro-1H-naphthalene-8,5'-oxolane]-2'-yl]acetate
• CAS: 170081-10-4
• 化学式: C₂₁H₃₄O₃
• 分子量: 334.499
• InChiKey: TWPKVIVCLJTFPY-OTNPHJDUSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  4.4
• 重原子数：
  24
• 可旋转键数：
  3
• 环数：
  3.0
• sp3杂化的碳原子比例：
  0.86
• 拓扑面积：
  35.5
• 氢给体数：
  0
• 氢受体数：
  3

反应信息

• 作为反应物：
  描述：

  methyl grindelate 在 溴 、 N-溴代乙酰胺 作用下， 以 水 、 丙酮 为溶剂， 反应 8.0h， 生成 methyl 2-((2R,3'S,4a'R,5R,8a'R)-3'-bromo-5,5',5',8a'-tetramethyl-2'-methylenedecahydro-2'H,3H-spiro[furan-2,1'-naphthalen]-5-yl)acetate
  参考文献：
  名称：

  Regio- and stereoselective hydroxylation of grindelic acid and its 3.ALPHA.-hydroxy derivative.

  摘要：

  通过分别给出的17-或7β-溴衍生物（6a，b或9a，b）在古二酸（1a）和3α-羟基古二酸（1b）的C-17或C-6位选择性地引入氢酰基通过与 Br2 或 NBA 溴化。 7β-羟基衍生物(17a,b)由8β-甲基-7-酮衍生物(14a,b)通过NaBH4还原得到。 7α-羟基衍生物(18a,b)是从在C-9位含有断裂结构的8,9-en-7-one衍生物(15a,b)选择性获得的。

  DOI：

  10.1248/cpb.39.2167
• 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 吡啶 、 4-二甲氨基吡啶 、 氢氧化钾 、 sodium hydroxide 、 氯化亚砜 、 4 A molecular sieve 、 双氧水 、 碘 、 pyridinium chlorochromate 、 diborane(6) 作用下， 以 二氯甲烷 为溶剂， 反应 20.0h， 生成 methyl grindelate
  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。
• Further diterpenes from plants of the compositae, subtribe solidagininae
  作者：J. Jakupovic、R.N. Baruah、C. Zdero、F. Eid、V.P. Pathak、T.V. Chau-thi、F. Bohlmann、R.M. King、H. Robinson

  DOI：10.1016/s0031-9422(00)81166-8

  日期：1986.7

  isolated from the aerial parts of Gutierrezia species and nine from Happlopappus pectinatus . Four neoclerodanes and a friedolabdane were obtained from the aerial parts of Haplopappus paucidentatus . From the Grindelia species, in addition to known derivatives of grindelic acid, an arabinoside was isolated. The absolute configuration of the ent -labdanes was determined by transformation of grindelic acid

  摘要 从Gutierrezia 种的地上部分分离得到6 个新的ent-labdanes，从Happlopappus pectinatus 分离得到9 个。从 Haplopappus paucidentatus 的地上部分获得了四种新克莱罗丹和一种弗里多拉丹。从 Grindelia 物种中，除了已知的 Grindelic 酸衍生物外，还分离出一种阿拉伯糖苷。ent-labdanes 的绝对构型是通过将甘地酸转化为甲基-6-氧代-7,8-二氢格林地酸来确定的，其中该构型是通过正棉花效应建立的。从一枝黄花中分离出一种新的松香烷衍生物。
• Stereocontrolled Synthesis of <i>ent</i>-Grindelic Acid. A Useful Example of Diastereofacial Guidance in an Oxonium Ion-Initiated Pinacolic Ring Expansion
  作者：Leo A. Paquette、Hui-Ling Wang

  DOI：10.1021/jo960547p

  日期：1996.1.1

  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.
• Regio- and stereoselective hydroxylation of grindelic acid and its 3.ALPHA.-hydroxy derivative.
  作者：Sayoko HIRANUMA、Takeshi SHIMIZU、Hirosuke YOSHIOKA

  DOI：10.1248/cpb.39.2167

  日期：——

  A hydrocyl group was selectively introduced at the C-17 or C-6 position of grindelic acid (1a) and 3α-hydroxygrindelic acid (1b) via the 17- or 7β-bromo derivatives (6a, b or 9a, b) given respectively by bromination with Br2 or NBA. The 7β-hydroxy derivatives (17a, b) were obtained via the 8β-methyl-7-one derivatives (14a, b) by reduction with NaBH4. The 7α-hydroxy derivatives (18a, b) were obtained selectively from the 8, 9-en-7-one derivatives (15a, b) which contain a cleaved structure at the C-9 position.

  通过分别给出的17-或7β-溴衍生物（6a，b或9a，b）在古二酸（1a）和3α-羟基古二酸（1b）的C-17或C-6位选择性地引入氢酰基通过与 Br2 或 NBA 溴化。 7β-羟基衍生物(17a,b)由8β-甲基-7-酮衍生物(14a,b)通过NaBH4还原得到。 7α-羟基衍生物(18a,b)是从在C-9位含有断裂结构的8,9-en-7-one衍生物(15a,b)选择性获得的。