eriocephalin | 71774-90-8

• 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: eriocephalin
• CAS: 71774-90-8
• 化学式: C₂₄H₃₀O₉
• 分子量: 462.497
• InChiKey: MVZLPYVWRQUGCU-QHBHDKJQSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  1.2
• 重原子数：
  33
• 可旋转键数：
  6
• 环数：
  5.0
• sp3杂化的碳原子比例：
  0.71
• 拓扑面积：
  125
• 氢给体数：
  1
• 氢受体数：
  9

反应信息

• 作为反应物：
  描述：

  eriocephalin 在 potassium tert-butylate 作用下， 以 氯仿 为溶剂， 反应 96.5h， 生成 5-(furan-3-yl)-7'-methyl-2'-oxo-2',3',4,4',5,5',5a',7'-octahydro-2H-spiro[furan-3,6'-naphtho[1,8-bc]furan]-2-yl acetate
  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

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。
• Hemisynthesis of some biogenetically anomalous 17β-neoclerodane diterpenoids
  作者：María J. Domínguez、Ekkehard Mössner、María C. de la Torre、Benjamín Rodríguez

  DOI：10.1016/s0040-4020(98)00890-4

  日期：1998.11

  neoclerodane framework. The acid catalysed nucleophilic substitution of a 20-O-acetyl group in 20,12-hemiacetals by a 20-O-methyl group was also studied. Other reactions (α-ketol rearrangements, formation of enol esters and reduction of diosphenol groups) as well as chemical correlations between several neoclerodanes were also carried out, providing useful data for the chemistry of these compounds. Finally

  已经研究了几种天然新环戊烷二萜类化合物（ereocephalin，isoeriocephalin，7,8-didehydroeriocephalin，picropolin和picropolinone）的反应性。碱性试剂催化的转化（在C-8上的顶基化，从C-7α到C-6α位置的反乙酰化，稳定的7α，19-半缩醛的形成以及7α，19-半缩醛和19-羟基-7-酮的互变异构混合物形式）在每种情况下都受到新环戊烷骨架C-20位置的功能和立体化学引起的空间和应变效应的影响。酸催化的20-的亲核取代ø -乙酰基组中的20,12-半缩醛通过20- Ô还研究了-甲基。还进行了其他反应（α-酮醇重排，烯醇酯的形成和二酚基团的还原）以及几种新环戊烷之间的化学相关性，为这些化合物的化学性质提供了有用的数据。最后，从6- O-乙酰基异脑脑素开始的丁烯半胱氨酸蛋白酶C的半合成支持了我们先前关于生物上异常的17β-新环戊烷二萜类化合物形成的假设。
• A chlorine-containing and two 17β-neo-clerodane diterpenoids from Teucrium polium subsp. Vincentinum
  作者：Maria C. Carreiras、Benjamín Rodríguez、Franco Piozzi、Giuseppe Savona、María R. Torres、Aurea Perales

  DOI：10.1016/s0031-9422(00)97764-1

  日期：——

  Abstract From the aerial parts of Teucrium polium subsp. vincentinum three new neo-clerodane diterpenoids, teuvincentins A, B and C, have been isolated besides four already known diterpenes (19-acetylgnaphalin, eriocephalin, isoeriocephalin and 3-deacetyl-20- epi -teulanigin) and the flavones cirsiliol and apigenin. The structures of teuvincentin A [(12 S , 20 S )-20- O -acetyl-19-acetoxy-18-chloro-15

  摘要来自 Teucrium polium subsp. 的地上部分。vincentinum 除了四种已知的二萜（19-乙酰脑啡肽、eriocephalin、isoeriocephalin 和 3-deacetyl-20-epi-teulanigin）和黄酮 cirsiliol 之外，还分离了三种新的新克罗丹二萜类化合物 teuvincentins A、B 和 C。teuvincentin A [(12 S , 20 S )-20-O-acetyl-19-acetoxy-18-chloro-15,16-epoxy-4α,7-dihydroxy-6-oxo-neo-clerodane-7, 13(16),14-triene-20,12-heemiacetal], B [12 S,20 S )-20-O-乙酰-4α,18;15,16-diepoxy-6α-hydroxy-17β-neo-clerodane
• Isoeriocephalin and 20-deacetyleriocephalin, Neoclerodane Diterpenoids from Teucrium lanigerum
  作者：Francisco Férnandez-Gadea、Benjamín Rodríguez、Giuseppe Savona、Franco Piozzi

  DOI：10.1016/s0031-9422(00)82621-7

  日期：1984.1
• Transformation of neoclerodane diterpenoids into 19-norneoclerodane derivatives
  作者：Gema Dominguez、Maria C. De la Torre、Benjamin Rodriguez

  DOI：10.1021/jo00023a027

  日期：1991.11

  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.