(2'S,3'R)-3'-hydroxymarmesin | 87725-60-8

• 分子结构分类: 有机化合物 - 苯丙烷和聚酮 - 香豆素及其衍生物
• 英文名称: (2'S,3'R)-3'-hydroxymarmesin
• 英文别名: Smyrindiol；(2S,3R)-3-hydroxy-2-(2-hydroxypropan-2-yl)-2,3-dihydrofuro[3,2-g]chromen-7-one
• CAS: 87725-60-8
• 化学式: C₁₄H₁₄O₅
• 分子量: 262.262
• InChiKey: AIQSGHBQRRSBCN-OLZOCXBDSA-N

物化性质

• 沸点：
  469.4±45.0 °C(Predicted)
• 密度：
  1.445±0.06 g/cm3(Predicted)

计算性质

• 辛醇/水分配系数(LogP)：
  1.4
• 重原子数：
  19
• 可旋转键数：
  1
• 环数：
  3.0
• sp3杂化的碳原子比例：
  0.36
• 拓扑面积：
  76
• 氢给体数：
  2
• 氢受体数：
  5

反应信息

• 作为反应物：
  描述：

  (2'S,3'R)-3'-hydroxymarmesin 在 三氟乙酸 作用下， 以 二氯甲烷 为溶剂， 反应 1.33h， 以100%的产率得到补骨脂素
  参考文献：
  名称：

  Synthesis of 2,3-Dihydro-3-hydroxy-2-hydroxylalkylbenzofurans from Epoxy Aldehydes. One-Step Syntheses of Brosimacutin G, Vaginidiol, Vaginol, Smyrindiol, Xanthoarnol, and Avicenol A. Biomimetic Syntheses of Angelicin and Psoralen

  摘要：

  [GRAPHICS]We have developed two practical one-step syntheses of 2,3-dihydro-3-hydroxy-2-hydroxyalkylbenzofurans from readily available optically pure alpha,beta-epoxy aldehydes. Electron-deficient resorcinols react with epoxy aldehydes using either Cs2CO3 in DMF or KOH/CaCl2 in MeOH to give adducts 13, 16, 18, 20, 21, and brosimacutin G (6t). Grignard reagents prepared by low-temperature halogen-metal exchange of acetoxy iodocoumarins 35d and 40 and acetoxy bromonaphthalene 41 add to epoxy aldehyde (S)-26 to complete the first syntheses of vaginidiol (7c), vaginol (7t), smyrindiol (8c), xanthoarnol (8t), and avicenol A (9t). Acid-catalyzed fragmentation of vaginidiol or vaginol provides angelicin, while that of smyrindiol or xanthoarnol affords psoralen. In both cases, the trans isomers fragment only twice as fast as the cis isomers, possibly through the intermediacy of a common benzylic cation. This may have implications for the biosynthesis of angelicin and psoralen.

  DOI：

  10.1021/jo047974k
• 作为产物：
  描述：

  (R)-2-(2-hydroxypropan-2-yl)-2H-furo[3,2-g]chromene-3,7-dione 在 sodium tetrahydroborate 作用下， 以 甲醇 为溶剂， 反应 1.5h， 以172 mg的产率得到(2'S,3'R)-3'-hydroxymarmesin
  参考文献：
  名称：

  Coumarins from Ferulago capillaris and F. brachyloba

  摘要：

  Four new coumarins, (+)-senecioylprangol, (-)-3 '-senecioyloxymarmesin, (+)-3 '-hydroxyprantschimgin and (+)-2"-senecioyloxymarmesin, besides 12 known coumarins have been isolated from two Ferulago species. Their structures have been established by spectroscopic methods and partial synthesis. New synthetic 3'-oxocoumarins are also described. There is a remarkable difference in the contents of the most abundant coumarins found in the roots of both species: osthol and aurapten are specific to F. capillaris and F. brachyloba, respectively. (C) 2000 Elsevier Science Ltd. All rights reserved.

  DOI：

  10.1016/s0031-9422(99)00524-5

文献信息

• Asymmetric total synthesis of smyrindiol employing an organocatalytic aldol key step
  作者：Dieter Enders、Jeanne Fronert、Tom Bisschops、Florian Boeck

  DOI：10.3762/bjoc.8.123

  日期：——

  The first organocatalytic asymmetric synthesis of smyrindiol, by using an (S)-proline catalyzed enantioselective intramolecular aldol reaction as the key step, is described. Smyrindiol was synthesized from commercially available 2,4-dihydroxybenzaldehyde in 15 steps, with excellent stereoselectivity (de = 99%, ee = 99%). In the course of this total synthesis a new and mild coumarin assembly was developed

  描述了通过使用 (S)-脯氨酸催化的对映选择性分子内醇醛反应作为关键步骤，首次有机催化不对称合成 smyrindiol。Smyrindiol 由市售的 2,4-二羟基苯甲醛分 15 步合成，具有出色的立体选择性（de = 99%，ee = 99%）。在该全合成过程中，开发了一种新的温和的香豆素组装体。
• Dihydrofurocoumarin glucosides from Angelica archangelica and Angelica silvestris
  作者：John Lemmich、Svend Havelund、Ole Thastrup

  DOI：10.1016/0031-9422(83)83044-1

  日期：1983.1

  A water-soluble root extract of Angelica archangelica subsp. litoralis afforded, in addition to adenosine, coniferin and the two known dihydrofurocoumarin glycosides, apterin and 1′-O-β-d-glycopyranosyl-(S)-marmesin (marmesinin), two new dihydrofuranocoumarin glycosides, 1′-O-β-d-glucopyranosyl-(2S, 3R)-3-hydroxymarmesin, and 2′-β-d-glucopyranosyloxymarmesin. For the latter a 2S-configuration was demonstrated

  当归亚种的水溶性根提取物。除了腺苷、针叶树素和两种已知的二氢呋喃香豆素糖苷 apterin 和 1'-O-β-d-吡喃糖基-(S)-marmesin (marmesinin) 外，liticalis 还提供了两种新的二氢呋喃香豆素糖苷 1'-O-β- d-吡喃葡萄糖基-(2S, 3R)-3-hydroxymarmesin 和 2'-β-d-glupyranosyloxymarmesin。对于后者，证明了 2S 构型，位置 1' 的立体化学仍未确定。A. silvestris 的根同样提供 1'-O-β-d-吡喃葡萄糖基-(2S, 3R)-3-hydroxymarmesin。通过与在这项工作中获得的苷元 2S,3R)-3-羟基marmesin 的相关性，建立了已知的二氢呋喃香豆素二酯 smirniorin 和 smirnioridin 的绝对构型 (2S,3R)。
• Coumarins from Ferulago capillaris and F. brachyloba
  作者：Benedicto Jiménez、Marı́a Concepción Grande、Josefa Anaya、Pascual Torres、Manuel Grande

  DOI：10.1016/s0031-9422(99)00524-5

  日期：2000.4

  Four new coumarins, (+)-senecioylprangol, (-)-3 '-senecioyloxymarmesin, (+)-3 '-hydroxyprantschimgin and (+)-2"-senecioyloxymarmesin, besides 12 known coumarins have been isolated from two Ferulago species. Their structures have been established by spectroscopic methods and partial synthesis. New synthetic 3'-oxocoumarins are also described. There is a remarkable difference in the contents of the most abundant coumarins found in the roots of both species: osthol and aurapten are specific to F. capillaris and F. brachyloba, respectively. (C) 2000 Elsevier Science Ltd. All rights reserved.
• Synthesis of 2,3-Dihydro-3-hydroxy-2-hydroxylalkylbenzofurans from Epoxy Aldehydes. One-Step Syntheses of Brosimacutin G, Vaginidiol, Vaginol, Smyrindiol, Xanthoarnol, and Avicenol A. Biomimetic Syntheses of Angelicin and Psoralen
  作者：Yefen Zou、Mercedes Lobera、Barry B. Snider

  DOI：10.1021/jo047974k

  日期：2005.3.1

  [GRAPHICS]We have developed two practical one-step syntheses of 2,3-dihydro-3-hydroxy-2-hydroxyalkylbenzofurans from readily available optically pure alpha,beta-epoxy aldehydes. Electron-deficient resorcinols react with epoxy aldehydes using either Cs2CO3 in DMF or KOH/CaCl2 in MeOH to give adducts 13, 16, 18, 20, 21, and brosimacutin G (6t). Grignard reagents prepared by low-temperature halogen-metal exchange of acetoxy iodocoumarins 35d and 40 and acetoxy bromonaphthalene 41 add to epoxy aldehyde (S)-26 to complete the first syntheses of vaginidiol (7c), vaginol (7t), smyrindiol (8c), xanthoarnol (8t), and avicenol A (9t). Acid-catalyzed fragmentation of vaginidiol or vaginol provides angelicin, while that of smyrindiol or xanthoarnol affords psoralen. In both cases, the trans isomers fragment only twice as fast as the cis isomers, possibly through the intermediacy of a common benzylic cation. This may have implications for the biosynthesis of angelicin and psoralen.