3,5,6-tris(1,1-dimethylallyloxy)-1-methoxyxanthen-9-one | 400008-15-3

• 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: 3,5,6-tris(1,1-dimethylallyloxy)-1-methoxyxanthen-9-one
• 英文别名: 1-Methoxy-3,5,6-tris(2-methylbut-3-en-2-yloxy)xanthen-9-one
• CAS: 400008-15-3
• 化学式: C₂₉H₃₄O₆
• 分子量: 478.585
• InChiKey: MZQYUXQOVRIQIH-UHFFFAOYSA-N

物化性质

• 沸点：
  576.2±50.0 °C(Predicted)
• 密度：
  1.104±0.06 g/cm3(Predicted)

计算性质

• 辛醇/水分配系数(LogP)：
  6.5
• 重原子数：
  35
• 可旋转键数：
  10
• 环数：
  3.0
• sp3杂化的碳原子比例：
  0.34
• 拓扑面积：
  63.2
• 氢给体数：
  0
• 氢受体数：
  6

反应信息

• 作为反应物：
  描述：

  3,5,6-tris(1,1-dimethylallyloxy)-1-methoxyxanthen-9-one 以 甲醇 、 水 为溶剂， 反应 0.05h， 以60%的产率得到1-O-methylforbesione
  参考文献：
  名称：

  微波辅助克莱森重排/狄尔斯-阿尔德级联反应合成笼状藤黄天然产物和类似物

  摘要：

  微波辅助 Claisen 重排/Diels-Alder 级联反应用于合成笼状藤黄天然产物和类似物，其中含有独特的 4-oxa-tricyclo[4.3.1.03,7]decan-2-one 支架，来自呫吨酮和色酮-基于基材。获得了福布松和丁酮以及两个新的和六个已知的笼状类似物。与传统的热法相比，在微波照射下反应时间大大缩短，收率大大提高。此外，在级联反应中观察到的区域选择性也得到了合理化。长期以来，藤黄因其愈合、抗菌和细胞毒性活性而被用于民间药物。

  DOI：

  10.3184/174751911x13191290708355
• 作为产物：
  描述：

  2,3,4-tris(benzyloxy)benzaldehyde 在 palladium on activated charcoal manganese(IV) oxide 、 氢氧化钾 、 正丁基锂 、 四丁基氟化铵 、 氢气 、 magnesium bromide 作用下， 以 四氢呋喃 、 甲醇 、 二氯甲烷 为溶剂， -78.0~25.0 ℃ 、101.33 kPa 条件下， 反应 11.75h， 生成 3,5,6-tris(1,1-dimethylallyloxy)-1-methoxyxanthen-9-one
  参考文献：
  名称：

  “Biomimetic” Cascade Reactions in Organic Synthesis: Construction of 4-Oxatricyclo[4.3.1.0]decan-2-one Systems and Total Synthesis of 1-O-Methylforbesione via Tandem Claisen Rearrangement/Diels-Alder Reactions

  摘要：

  A further demonstration of the value of "biomimetically" inspired synthetic strategies toward natural products is provided by the title reactions that were developed for the construction of 4-oxatricyclo[4.3.1.0]decan-2-one systems from prochiral aromatic precursors. This biomimetic cascade was applied to the synthesis of 1-O-methylforbesione (2) from the prenylated xanthone 1 in one pot.

  DOI：

  10.1002/1521-3773(20011119)40:22<4264::aid-anie4264>3.0.co;2-1

文献信息

• Biomimetic total synthesis of forbesione and desoxymorellin utilizing a tandem Claisen/Diels–Alder/Claisen rearrangement
  作者：Eric J. Tisdale、Irina Slobodov、Emmanuel A. Theodorakis

  DOI：10.1039/b311833a

  日期：——

  A concise synthesis of forbesione (1) and desoxymorellin (3) is presented. Central to the strategy is a biomimetic Claisen/Diels–Alder/Claisen reaction cascade that proceeds in a regioselective manner and produces the desired scaffold exclusively. The observed regioselectivity and product distribution of the Claisen/Diels–Alder/Claisen reaction are attributed to the electronic effects of the xanthone oxygen (O10), the C9 carbonyl group and the nature of the C1 functionality.

  本文介绍了福尔酮（1）和脱氧毛蕊花素（3）的简明合成方法。该策略的核心是仿生物的 Claisen/DielsâAlder/Claisen 级联反应，该反应以区域选择性的方式进行，并完全生成所需的支架。观察到的 Claisen/DielsâAlder/Claisen 反应的区域选择性和产物分布归因于氧杂蒽酮（O10）、C9 羰基和 C1 官能团性质的电子效应。
• “Biomimetic” Cascade Reactions in Organic Synthesis: Construction of 4-Oxatricyclo[4.3.1.0]decan-2-one Systems and Total Synthesis of 1-O-Methylforbesione via Tandem Claisen Rearrangement/Diels-Alder Reactions
  作者：K. C. Nicolaou、Jim Li

  DOI：10.1002/1521-3773(20011119)40:22<4264::aid-anie4264>3.0.co;2-1

  日期：2001.11.19

  A further demonstration of the value of "biomimetically" inspired synthetic strategies toward natural products is provided by the title reactions that were developed for the construction of 4-oxatricyclo[4.3.1.0]decan-2-one systems from prochiral aromatic precursors. This biomimetic cascade was applied to the synthesis of 1-O-methylforbesione (2) from the prenylated xanthone 1 in one pot.
• Microwave-Assisted Claisen Rearrangement/Diels–Alder Cascade reaction for the Synthesis of Caged <i>Garcinia</i> Natural Products and Analogues
  作者：Xiang Li、Xiaojin Zhang、Zhuoqin Yu、Xiaorong Liu、Qidong You、Qinglong Guo

  DOI：10.3184/174751911x13191290708355

  日期：2011.11

  and six known caged analogues were obtained. Compared with the traditional thermal method, the reaction time was reduced dramatically and the yield was greatly improved under microwave irradiation. In addition, the regioselectivity observed in the cascade reaction has also been rationalised. Garcinia have long been used in folk medicines for their healing, antibacterial, and cytotoxic activities.

  微波辅助 Claisen 重排/Diels-Alder 级联反应用于合成笼状藤黄天然产物和类似物，其中含有独特的 4-oxa-tricyclo[4.3.1.03,7]decan-2-one 支架，来自呫吨酮和色酮-基于基材。获得了福布松和丁酮以及两个新的和六个已知的笼状类似物。与传统的热法相比，在微波照射下反应时间大大缩短，收率大大提高。此外，在级联反应中观察到的区域选择性也得到了合理化。长期以来，藤黄因其愈合、抗菌和细胞毒性活性而被用于民间药物。