(3S,3aR,7S,8aS,Z)-3,7-dimethyl-6-vinyl-3a,4,8,8a-tetrahydro-3H-cyclohepta[b]furan-2(7H)-one | 862387-29-9

• 分子结构分类: 有机化合物 - 有机杂环化合物 - 内酯类
• 英文名称: (3S,3aR,7S,8aS,Z)-3,7-dimethyl-6-vinyl-3a,4,8,8a-tetrahydro-3H-cyclohepta[b]furan-2(7H)-one
• 英文别名: (3S,3aR,7S,8aS)-3,7-dimethyl-6-vinyl-3,3a,4,7,8,8a-hexahydro-2H-cyclohepta[b]furan-2-one；11α,13-dihydroxanthatin；(3S,3aR,7S,8aS)-6-ethenyl-3,7-dimethyl-3,3a,4,7,8,8a-hexahydrocyclohepta[b]furan-2-one
• CAS: 862387-29-9
• 化学式: C₁₃H₁₈O₂
• 分子量: 206.285
• InChiKey: QQPKFFIULVROQD-XPXLGCRWSA-N

物化性质

• 熔点：
  82.5-83.5 °C
• 沸点：
  337.2±41.0 °C(Predicted)
• 密度：
  1.041±0.06 g/cm3(Predicted)

计算性质

• 辛醇/水分配系数(LogP)：
  2.9
• 重原子数：
  15
• 可旋转键数：
  1
• 环数：
  2.0
• sp3杂化的碳原子比例：
  0.62
• 拓扑面积：
  26.3
• 氢给体数：
  0
• 氢受体数：
  2

反应信息

• 作为反应物：
  描述：

  (3S,3aR,7S,8aS,Z)-3,7-dimethyl-6-vinyl-3a,4,8,8a-tetrahydro-3H-cyclohepta[b]furan-2(7H)-one 在 Hoveyda-Grubbs catalyst second generation 、 双氧水 、 溶剂黄146 、 lithium diisopropyl amide 作用下， 以 四氢呋喃 、 二氯甲烷 为溶剂， 反应 7.33h， 生成 xanthatin
  参考文献：
  名称：

  仿生合成：黄嘌呤二聚体的发现

  摘要：

  从黄嘌呤开始，仿生合成了一种新型的单体黄原酸酯4β，5β-环氧黄嘌呤-1α，4α-过氧化物。此外，黄嘌呤素的三种不同二聚化以头对头或头尾相接的方式合成了四个前所未有的黄原酸内酯二聚体。值得注意的是，这些二聚体化合物首先在实验室中被鉴定为人工制品，其中两种化合物，Mogolides A和B被证明是Xanthium mogolium Kitag植物中的天然产物。

  DOI：

  10.1002/anie.201406461
• 作为产物：
  描述：

  (S,E)-7-(tert-butyldimethylsilyloxy)-6-methylhept-2-en-4-one 在 RuCl2(1,3-dimesityl-imidazolidin-2-yl)(PCy3)(=CHPh) 、 palladium diacetate 吡啶 、 9-borabicyclo[3.3.1]nonane dimer 、 copper diacetate 、 dimethyl sulfide borane 、 potassium tert-butylate 、 四丁基氟化铵 、 铬酸 、 戴斯-马丁氧化剂 、 (R)-2-甲基-CBS-恶唑硼烷 、 lithium diisopropyl amide 作用下， 以 四氢呋喃 、 正己烷 、 二氯甲烷 、 丙酮 、 甲苯 、 乙腈 为溶剂， 反应 30.58h， 生成 (3S,3aR,7S,8aS,Z)-3,7-dimethyl-6-vinyl-3a,4,8,8a-tetrahydro-3H-cyclohepta[b]furan-2(7H)-one
  参考文献：
  名称：

  Asymmetric Synthesis of (−)-Dihydroxanthatin by the Stereoselective Oshima−Utimoto Reaction

  摘要：

  The catalytic stereoselective Oshima-Utimoto reaction is useful for the construction of five-membered oxacycles from simple starting materials and was employed for the preparation of the lactone group in the asymmetric synthesis of (-)-11 alpha,13-dihydroxanthatin. Completion of the synthesis is facilitated by ring-closing enyne metathesis and alkene cross metathesis reactions.

  DOI：

  10.1021/ol051276k

文献信息

• Enantioselective and Collective Syntheses of Xanthanolides Involving a Controllable Dyotropic Rearrangement of cis-β-Lactones
  作者：Weiwu Ren、Yichao Bian、Ziyang Zhang、Hai Shang、Pengtao Zhang、Yuejie Chen、Zhen Yang、Tuoping Luo、Yefeng Tang

  DOI：10.1002/anie.201202643

  日期：2012.7.9

  atom‐economic, enantio‐, and diastereoselective synthetic route to trisubstituted γ‐butyrolactones based on a Wagner–Meerwein‐type dyotropic rearrangement of cis‐β‐lactones is described (see scheme). This methodology was applied in efficient and protecting‐group‐free formal syntheses and total syntheses of various xanthanolide natural products.

  让我们交换一下：描述了一种基于Wagner-Meerwein型顺式-β-内酯重排的可扩展，原子经济，对映和非对映选择性的合成三取代γ-丁内酯的方法（参见方案）。该方法学被用于各种黄原醇天然产物的高效且无保护基团的形式合成和总合成中。
• Total synthesis of (−)-xanthatin
  作者：Hiromasa Yokoe、Masahiro Yoshida、Kozo Shishido

  DOI：10.1016/j.tetlet.2008.03.081

  日期：2008.5

  The first enantioselective total synthesis of xanthatin, a xanthanolide sesquiterpenoid exhibiting potent antibacterial activity against MRSA, has been accomplished from an optically pure bicyclic lactone, previously synthesized by our group.

  黄嘌呤酮的第一种对映选择性全合成是一种黄嘌呤类倍半萜类化合物，对MRSA表现出强效的抗菌活性，它是由我们小组先前合成的光学纯的双环内酯完成的。
• Asymmetric total syntheses of xanthatin and 11,13-dihydroxanthatin using a stereocontrolled conjugate allylation to γ-butenolide
  作者：Kenji Matsumoto、Kuniyoshi Koyachi、Mitsuru Shindo

  DOI：10.1016/j.tet.2012.11.077

  日期：2013.1

  The stereocontrolled conjugate allylation to an optically pure gamma-butenolide provided direct and reliable access to a trans-fused series of xanthanolide sesquiterpenoids and allowed for the enantioselective total syntheses of xanthatin and 11,13-dihydroxanthatin to be efficiently achieved. (C) 2012 Elsevier Ltd. All rights reserved.
• Total synthesis of xanthanolides
  作者：Kazumasa Matsuo、Keiko Ohtsuki、Takashi Yoshikawa、Kozo Shishido、Kaori Yokotani-Tomita、Mitsuru Shindo

  DOI：10.1016/j.tet.2010.08.061

  日期：2010.10

  The total synthesis and determination of the absolute configuration of (+)- and (-)-sundiversifolide have been achieved via intramolecular acylation and Wittig-lactonization as the key steps. The xanthanolide sesquiterpene lactones, 8-epi-xanthatin (1), dihydroxanthatin (2), and xanthatin (3) were also prepared, starting from a common intermediate derived from the synthesis of sundiversifolide. (C) 2010 Elsevier Ltd. All rights reserved.
• Asymmetric Synthesis of (−)-Dihydroxanthatin by the Stereoselective Oshima−Utimoto Reaction
  作者：Michael A. Evans、James P. Morken

  DOI：10.1021/ol051276k

  日期：2005.7.1

  The catalytic stereoselective Oshima-Utimoto reaction is useful for the construction of five-membered oxacycles from simple starting materials and was employed for the preparation of the lactone group in the asymmetric synthesis of (-)-11 alpha,13-dihydroxanthatin. Completion of the synthesis is facilitated by ring-closing enyne metathesis and alkene cross metathesis reactions.