rac-(6aR,11aR)-8-hydroxy-3,9-dimethoxypterocarpan | 152611-67-1

• 分子结构分类: 有机化合物 - 苯丙烷和聚酮 - 异黄酮类化合物
• 英文名称: rac-(6aR,11aR)-8-hydroxy-3,9-dimethoxypterocarpan
• 英文别名: (6aS,11aS)-3,9-dimethoxy-6a,11a-dihydro-6H-[1]benzofuro[3,2-c]chromen-8-ol
• CAS: 152611-67-1
• 化学式: C₁₇H₁₆O₅
• 分子量: 300.311
• InChiKey: KIKDCPYSYOMXEJ-SJKOYZFVSA-N

物化性质

• 沸点：
  439.8±45.0 °C(Predicted)
• 密度：
  1.312±0.06 g/cm3(Predicted)

计算性质

• 辛醇/水分配系数(LogP)：
  2.6
• 重原子数：
  22
• 可旋转键数：
  2
• 环数：
  4.0
• sp3杂化的碳原子比例：
  0.29
• 拓扑面积：
  57.2
• 氢给体数：
  1
• 氢受体数：
  5

反应信息

• 作为反应物：
  描述：

  rac-(6aR,11aR)-8-hydroxy-3,9-dimethoxypterocarpan 生成 3,9-Dimethoxy-6a,11a-cis-dihydro-6H-benzofuro<3,2-c><1>benzopyran-8-ol Trifluoromethanesulfonate
  参考文献：
  名称：

  ENGLER, THOMAS A.;COMBRINK, KEITH D.;REDDY, JAYACHANDRA P., J. CHEM. SOC. CHEM. COMMUN.,(1989) N, C. 454-455

  摘要：

  DOI：
• 作为产物：
  描述：

  2-甲氧基对苯二酚 在 sodium sulfate 、 zinc(II) chloride 、 silver(l) oxide 作用下， 以 二氯甲烷 、 苯 为溶剂， 反应 2.25h， 生成 rac-(6aR,11aR)-8-hydroxy-3,9-dimethoxypterocarpan
  参考文献：
  名称：

  黄檀中具有生物活性的罗汉果，异黄烷和异黄烷的总合成

  摘要：

  通过对黄檀天然产物的生物筛选发现，（6a R，11a R）-3,8-二羟基-9-甲氧基翼果烷和（3 R）-7,2'-二羟基-4'，5'-二甲氧基异黄酮明显增加真皮乳头细胞的增殖和皮下注射这些化合物会在动物模型中诱发毛发周期的毛发生长。这些有趣的生物学活动促使我们设计了一条合成这些天然产物的实用途径，以进行进一步的药理评估。在这里我们报告了自然产生的罗汉果（（6a R，11a R）‐3,8‐dihydroxy‐9‐甲氧基罗汉果），异黄烷（（3 R）-5'-甲氧基维他命醇）和外消旋形式的异黄烷酮（（3 R）-7,2'-二羟基-4'，5'-二甲氧基异黄酮）。轻度的ZnCl 2介导的[3 + 2]环化方法与色酮和2-甲氧基-1,4-苯醌一起以单锅法构造了罗汉木骨架。O-甲基化和苄基C-O键的还原性裂解提供了5'-甲氧基vestitol，通过包括DDQ介导的三步序列将其转化为异黄酮，7,2'-二羟基-4'，5'-二甲氧基异黄酮苄基氧化。

  DOI：

  10.1002/bkcs.11375

文献信息

• A new regioselective synthesis of pterocarpans
  作者：Thomas A. Engler、Keith D. Combrink、Jayachandra P. Reddy

  DOI：10.1039/c39890000454

  日期：——

  Pterocarpans are formed directly and efficiently via titanium(IV) catalysed reactions of 2H-chromenes and 2-alkoxy-1,4-benzoquinones.

  通过2 H-色烯与2-烷氧基-1,4-苯醌的钛（IV）催化反应可直接有效地形成紫檀果。
• Insect Antifeedants, Pterocarpans and Pterocarpol, in Heartwood of<i>Pterocarpus macrocarpus</i>Kruz.
  作者：Masanori MORIMOTO、Hiromi FUKUMOTO、Masaru HIRATANI、Warinthorn CHAVASIRI、Koichiro KOMAI

  DOI：10.1271/bbb.60017

  日期：2006.8.23

  The insect antifeedant activities of pterocarpans and a sesquiterpene alcohol from the dichloromethane extract of Pterocarpus macrocarpus Kruz. (Leguminosae) were evaluated against the common cutworm, Spodoptera litura F. (Noctuidae), and the subterranean termite, Reticulitermes speratus (Kolbe)(Rhinotermitidae). Three pterocarpans, (−)-homopterocarpin (1), (−)-pterocarpin (2), and (−)-hydroxyhomopterocarpin (3) and the sesquiterpene alcohol, (+)-pterocarpol (5), were isolated from the dichloromethane extract of the heartwood of P. macrocarpus under guidance by a biological assay. Among these natural products, the most active insect antifeedant against both S. litura and R. speratus was 1. On the other hand, sesquiterpene alcohol 5 showed less insect antifeedant activity than the other pterocarpans against both insect species. While its methylated derivative, (−)-methoxyhomopterocarpin (4), showed high biological activity, 3 showed less insect antifeedant activity in this study. Interestingly, racemic 1 did not show insect antifeedant activity against S. litura. However, all of the test pterocarpans and isoflavones showed antifeedant activity against the test termites. Additionally, since these compounds were major constituents of P. macrocarpus, these antifeedant phenolics may act as chemical defense factors in this tree. In Thailand, lumber made from this tree is used to make furniture and in building construction due to its resistance to termite attack.

  对来自大果紫檀（Pterocarpus macrocarpus Kruz.）二氯甲烷提取物的紫檀苷和倍半萜醇（豆科）的昆虫拒食活性进行了评估，以对抗普通切根虫斜纹夜蛾（Spodoptera litura F.）（夜蛾科）和地下白蚁（Reticulitermes speratus (Kolbe)）（鼻白蚁科）。在生物测定指导下，从大果紫檀心材的二氯甲烷提取物中分离出三种紫檀苷（-）-紫檀苷（1）、（-）-紫檀苷（2）和（-）-羟基紫檀苷（3）以及倍半萜醇（+）-紫檀醇（5）。在这些天然产物中，对斜纹夜蛾和R. speratus最有效的昆虫拒食剂是1。另一方面，倍半萜醇5对这两种昆虫的昆虫拒食活性低于其他紫檀苷。虽然其甲基化衍生物（-）-甲氧基紫檀苷（4）显示出高生物活性，但在这项研究中，3的昆虫拒食活性较低。有趣的是，外消旋1对斜纹夜蛾没有表现出昆虫拒食活性。然而，所有
• Engler, Thomas A.; Letavic, Michael A.; Reddy, Jayachandra P., Journal of the American Chemical Society, 1991, vol. 113, # 13, p. 5068 - 5070
  作者：Engler, Thomas A.、Letavic, Michael A.、Reddy, Jayachandra P.

  DOI：——

  日期：——
• Formal 2 + 2 and 3 + 2 cycloaddition reactions of 2H-chromenes with 2-alkoxy-1,4-benzoquinones: regioselective synthesis of substituted pterocarpans
  作者：Thomas A. Engler、Jayachandra P. Reddy、Keith D. Combrink、David Vander Velde

  DOI：10.1021/jo00291a027

  日期：1990.2
• Asymmetric Reactions of 2-Methoxy-1,4-benzoquinones with Styrenyl Systems:  Enantioselective Syntheses of 8-Aryl-3-methoxybicyclo[4.2.0]oct-3-en-2,5-diones, 7-Aryl-3-hydroxybicyclo[3.2.1]oct-3-en-2,8-diones, 2-Aryl-6-methoxy-2,3-dihydrobenzofuran-5-ols, and Pterocarpans
  作者：Thomas A. Engler、Michael A. Letavic、Rajesh Iyengar、Kenneth O. LaTessa、Jayachandra P. Reddy

  DOI：10.1021/jo982164s

  日期：1999.4.1

  Reactions of 2-methoxy-1,4-benzoquinones 2 and 3 with (E)-propenylbenzenes 1 promoted at -78 degrees C by Ti(IV)-TADDOLates prepared from diol-(+)- 4 afford (1R,6R,7R,8R)-8-aryl-3-methoxy-7methylbicyclo[4.2.0]oct-3-en-2,5-diones 5/8 or (1R,5R,6R,7R)-7-aryl-3-hydroxy-6-methylbicyclo-3-en-2,8-diones 7/10 in good yield and high ee. (2S,3S)-2-Aryl-6-methoxy-3-methyl-2,3-dihydrobenzofuran-5-ols 6/9 are also found, but in slightly lower ee. Cyclobutanes 5/8 cleanly and efficiently rearrange to the dihydrobenzofurans 6/9 without loss of enantiomeric purity upon treatment with the Ti-TADDOLates at higher temperatures. Reactions of (Z)-propenylbenzene 17 and of indene with 2 and 3 give products in moderate enantiomeric purity. Products obtained from reactions of 1-anisylcycloalkenes with 2 differ significantly in yield and enantiomeric purity. In the latter reactions, the ee's of the cyclobutane products are consistently much higher than those of the dihydrobenzofuran products. More significantly, products of different absolute configuration result from different cycloalkenes. With 1-anisylcyclopentene or 1-anisylcyclohexene, all of the products are of similar configuration and are obtained in comparable yields and ee's. However, 1-anisylcycloheptene affords products that are diastereomeric with those of the 1-anisylcyclopentene, and in lower ee's. A mechanistic model is proposed. Application of these reactions to the enantioselective synthesis of the pterocarpan class of isoflavonoid natural products is also reported.