(12S,20S)-7α,19-Diacetoxy-20-O-acetyl-4α,18;15,16-diepoxy-6α-hydroxyneoclerodane-13(16),14-diene 20,12-hemiacetal | 92632-30-9

• 分子结构分类: 有机化合物 - 有机酸及其衍生物 - 羧酸及其衍生物
• 英文名称: (12S,20S)-7α,19-Diacetoxy-20-O-acetyl-4α,18;15,16-diepoxy-6α-hydroxyneoclerodane-13(16),14-diene 20,12-hemiacetal
• CAS: 92632-30-9
• 化学式: C₂₆H₃₄O₁₀
• 分子量: 506.55
• InChiKey: RIVDPUKWGXSXLB-PIRITQDHSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  2.68
• 重原子数：
  36.0
• 可旋转键数：
  5.0
• 环数：
  5.0
• sp3杂化的碳原子比例：
  0.73
• 拓扑面积：
  134.03
• 氢给体数：
  1.0
• 氢受体数：
  10.0

反应信息

• 作为反应物：
  描述：

  (12S,20S)-7α,19-Diacetoxy-20-O-acetyl-4α,18;15,16-diepoxy-6α-hydroxyneoclerodane-13(16),14-diene 20,12-hemiacetal 在 potassium tert-butylate 作用下， 以 四氢呋喃 为溶剂， 反应 0.33h， 以90%的产率得到5-(furan-3-yl)-4a'-(hydroxymethyl)-2'-methyldecahydro-2H-dispiro[furan-3,1'-naphthalene-5',2''-oxirane]-2,3',4'-triyl triacetate
  参考文献：
  名称：

  Transformation of neoclerodane diterpenoids into 19-norneoclerodane derivatives

  摘要：

  The neoclerodane diterpenoid eriocephalin (1) was transformed into its 19-nor derivatives 3 and 4 by reaction with potassium tert-butoxide in THF, whereas with the same treatment compound 6 yielded only the transacetylation derivative 7. These results indicated that 19-acetoxy-4-alpha,18-epoxy-7-alpha-hydroxy-6-oxoneoclerodane derivatives are transformed into the corresponding 19-nor compounds in a retroaldol reaction by loss of the C-19 carbon as formaldehyde followed by opening of the oxirane ring and intramolecular attack by a C-18 alkoxide on the carbonyl C-6 carbon atom, giving the allylic hemiacetal 3, which is easily dehydrated to the furanic derivative 4. Compound 4 was transformed into the alpha,beta-unsaturated gamma,delta-enol gamma-lactone 8 by an oxidation reaction with atomspheric oxygen in chloroform solution. Alternatively, it gave the alpha,beta-unsaturated gamma-lactone 11 under acid catalysis. These reactions allowed the partial syntheses of the naturally occurring diterpenoids teuscorolide (9) and teucvin (12) and are of interest for chemical transformations of substances of this kind.

  DOI：

  10.1021/jo00023a027
• 作为产物：
  描述：

  20-deacetyleriocephalin 在 吡啶 、 sodium tetrahydroborate 作用下， 以 甲醇 为溶剂， 反应 24.0h， 生成 (12S,20S)-7α,19-Diacetoxy-20-O-acetyl-4α,18;15,16-diepoxy-6α-hydroxyneoclerodane-13(16),14-diene 20,12-hemiacetal
  参考文献：
  名称：

  Isoeriocephalin and 20-deacetyleriocephalin, Neoclerodane Diterpenoids from Teucrium lanigerum

  摘要：

  DOI：

  10.1016/s0031-9422(00)82621-7

文献信息

• Some remarkable reactions of the diterpene eriocephalin: Neo-clerodane derivatives with insect antifeedant activity
  作者：María C. de la Torre、Gema Domínguez、Benjamín Rodríguez、Aurea Perales、Monique S.J. Simmonds、Wally M. Blaney

  DOI：10.1016/s0040-4020(01)89361-3

  日期：1994.1

  Base-catalyzed reaction of the neo-clerodane diterpenoid eriocephalin (1) gave the derivatives 3 and 4. The formation of these compounds implies an elimination of the C-19 carbon atom of 1 as formaldehyde by a reaction and, in the case of 4, subsequent reaction of this formaldehyde with the 18-alkoxide intermediate followed by an intramolecular and stereoselective 1,4-addition of the resulting C-18-oxa-methylene

  新环戊烷二萜类脑啡肽的碱催化反应（1）得到衍生物3和4。这些化合物的形成意味着通过反应消除了作为甲醛的1的C-19碳原子，在4的情况下，该甲醛与18醇盐中间体的随后反应是分子内和立体选择性1,4 -生成的C-18-氧杂亚甲基醇盐的加成。用碱处理eriocephalin 9的衍生物可产生转乙酰基化和水解产物（10-14），并在C-20不对称中心处颠倒配置。还报道了这些转化的机理方面以及在生物学测定中作为这些新环戊烷衍生物的昆虫拒食剂获得的结果。