enokipodin A | 306951-07-5

• 分子结构分类: 有机化合物 - 有机杂环化合物 - 苯并吡喃
• 英文名称: enokipodin A
• 英文别名: (1R,9R)-1,5,12,12-tetramethyl-8-oxatricyclo[7.2.1.02,7]dodeca-2(7),3,5-triene-4,9-diol
• CAS: 306951-07-5
• 化学式: C₁₅H₂₀O₃
• 分子量: 248.322
• InChiKey: KANVQRLDTGOSBL-HUUCEWRRSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  3.2
• 重原子数：
  18
• 可旋转键数：
  0
• 环数：
  3.0
• sp3杂化的碳原子比例：
  0.6
• 拓扑面积：
  49.7
• 氢给体数：
  2
• 氢受体数：
  3

反应信息

• 作为反应物：
  描述：

  enokipodin A 以 氯仿 为溶剂， 生成 enokipodin B
  参考文献：
  名称：

  Highly oxidized cuparene-type sesquiterpenes from a mycelial culture of Flammulina velutipes

  摘要：

  Cuparene-type sesquiterpenes were isolated from a culture broth of Flammulina velutipes (Curt.:Fr.) Sing. Using spectroscopic methods (HR-MS,H-1 and C-13 NMR, and 2D NMR, spectroscopy), their structures were determined to be 2,3,4,5-tetrahydro-2,7-dihydroxy-5,8,10,10-tetramethyl-2,5-methano-1-benzoxepin and 5-methyl-2-(3-oxo-1,2,2-trimethylcyclopentyl)benzoquinone. Both showed antimicrobial activity against Cladosporium herbarum and Bacillus subtilis. (C) 2000 Elsevier Science Ltd. All rights reserved.

  DOI：

  10.1016/s0031-9422(00)00189-8
• 作为产物：
  描述：

  (4R)-4-(2,5-dimethoxy-4-methylphenyl)-4,5,5-trimethyl-2-cyclopentenone 在 palladium on activated charcoal sodium dithionite 、 ammonium cerium(IV) nitrate 、 氢气 作用下， 以 乙醇 、 水 、 乙酸乙酯 、 乙腈 为溶剂， 反应 17.0h， 生成 enokipodin A
  参考文献：
  名称：

  对映体全合成的enokipodins AD，蘑菇，金针菇产生的抗菌倍半萜。

  摘要：

  （2,5-二甲氧基-4-甲基苯基）乙酸甲酯的总收率为8-28％，首次完成了对烯基足蛋白A，B，C和D的对映选择性全合成，这是一种具有抗微生物活性的高度氧化的α-cuparenone型倍半萜。通过应用Meyers的非对映选择性烷基化方案构建其C7-季不对称中心。本合成法证实了烯基鬼臼肽的绝对构型，并且还构成了（S）-1，4-异丙基二醇和（S）-Cuparene-1，4-醌的形式对映选择性合成。

  DOI：

  10.1271/bbb.69.374

文献信息

• Enantioselective palladium catalyzed conjugate additions of ortho-substituted arylboronic acids to β,β-disubstituted cyclic enones: total synthesis of herbertenediol, enokipodin A and enokipodin B
  作者：Jeffrey Buter、Renée Moezelaar、Adriaan J. Minnaard

  DOI：10.1039/c4ob01085j

  日期：——

  Palladium catalyzed asymmetric conjugate addition of ortho-substituted arylboronic acids to cyclic enones and its application in natural product synthesis.

  钯催化的手性共轭加成，将邻位取代的芳基硼酸加到环状烯酮上，并在天然产物合成中的应用。
• Palladium (II) catalyzed 5-endo epoxynitrile cyclizations: total syntheses of enokipodins A and B
  作者：Jesús Armando Luján-Montelongo、José G. Ávila-Zárraga

  DOI：10.1016/j.tetlet.2010.02.072

  日期：2010.4

  New total syntheses of the cuparenic sesquiterpenes enokipodins A and B were accomplished. The key step involves a novel, cationic-controlled and palladium (II) improved, 5-endo cyclization of an α-aryl-δ-epoxynitrile. The cyclization occurs with unmatched regioselectivity and high stereoselectivity. The synthesis is completed in 5 steps achieving yields of 50% for enokipodin A and 55% for enokipodin

  合成了新的全合成的伞形倍半萜烯烯配体A和B。的关键步骤涉及一种新颖的，阳离子控制和钯（II）改善，5-内切α-芳基δ-epoxynitrile的环化。环化反应具有无与伦比的区域选择性和高立体选择性。合成过程分5个步骤完成，对于enokipodin A，产率为50％，对于enokipodin B，产率为55％。
• Synthesis of Cyclopentenones with C4-Quaternary Stereocenters via Stereospecific [3,3]-Sigmatropic Rearrangement and Applications in Total Synthesis of Sesquiterpenoids
  作者：Weiping Zhou、Arnaud Voituriez

  DOI：10.1021/jacs.1c07966

  日期：2021.10.27

  A cationic gold(I)-catalyzed asymmetric [3,3]-sigmatropic rearrangement of sulfonium leads after cyclization to cyclopentenones with a C4-quaternary stereocenter. Starting with simple vinyl sulfoxides and propargyl silane, numerous compounds were isolated with moderate to good yields and excellent enantiomeric excesses (26 examples). The application of this simple methodology allowed the efficient

  锍的阳离子金 (I) 催化不对称 [3,3]-σ 重排在环化后生成具有 C4-季立体中心的环戊烯酮。从简单的乙烯基亚砜和炔丙基硅烷开始，以中等至良好的收率和优异的对映异构体过量分离了许多化合物（26 个实例）。应用这种简单的方法可以有效地合成五种天然倍半萜类化合物，包括 enokipodin A 和 B、hitoyopodin A、lagopodin A 和 isocuparene-3,4-diol。
• Enantioselective total synthesis of enokipodins A–D
  作者：Shigefumi Kuwahara、Mana Saito

  DOI：10.1016/j.tetlet.2004.04.191

  日期：2004.6

  The first enantioselective total synthesis of enokipodins A–D, highly oxidized α-cuparenone-type sesquiterpenoids with antimicrobial activity, was accomplished by using Meyers' diastereoselective alkylation protocol for the construction of the C7-quaternary asymmetric center. The present synthesis also constitutes a formal enantioselective synthesis of (S)-1,4-cuparenediol and (S)-cuparene-1,4-quinone

  利用Meyers的非对映选择性烷基化方案构建C7季不对称中心，完成了首个对映体全合成的烯基鬼臼草碱A–D，高度氧化的具有抗微生物活性的α-cuparenone型倍半萜。本合成也构成（正式对映选择性合成小号）-1,4- cuparenediol和（小号）-cuparene-1,4-醌。
• Srikrishna; Rao, M. Srinivasa, Indian Journal of Chemistry - Section B Organic and Medicinal Chemistry, 2010, vol. 49, # 10, p. 1363 - 1371
  作者：Srikrishna、Rao, M. Srinivasa

  DOI：——

  日期：——