(1SR,2RS,7SR,8RS)-4-oxatricyclo[6.2.1.0^2,7]undec-8-en-3-one | 99128-18-4

• 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: (1SR,2RS,7SR,8RS)-4-oxatricyclo[6.2.1.0^2,7]undec-8-en-3-one
• 英文别名: 5,8-methano-3,4,4a,5,8,8a-hexahydro-1H-2-benzopyran-1-one；(1S,2R,7S,8R)-4-oxatricyclo[6.2.1.02,7]undec-9-en-3-one
• CAS: 99128-18-4
• 化学式: C₁₀H₁₂O₂
• 分子量: 164.204
• InChiKey: QNSMRPGTIDIGLR-UYXSQOIJSA-N

物化性质

• 沸点：
  314.0±41.0 °C(Predicted)
• 密度：
  1.189±0.06 g/cm3(Predicted)

计算性质

• 辛醇/水分配系数(LogP)：
  1.5
• 重原子数：
  12
• 可旋转键数：
  0
• 环数：
  3.0
• sp3杂化的碳原子比例：
  0.7
• 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：

  (1SR,2RS,7SR,8RS)-4-oxatricyclo[6.2.1.0^2,7]undec-8-en-3-one 在 palladium on activated charcoal sodium tetrahydroborate 、 草酰氯 、 氢气 作用下， 以 乙醚 、 乙酸乙酯 、 苯 为溶剂， 反应 9.5h， 生成 2-<(diazomethylene)carbonyl>-3-<2-(phenylseleno)ethyl>bicyclo<2.2.1>heptane
  参考文献：
  名称：

  Reductive, radical-induced cyclization of 5-hexenals as a biomimetic model of the chemistry of secologanin formation

  摘要：

  DOI：

  10.1021/jo00225a042
• 作为产物：
  描述：

  5,6-dihydro-pyran-2-one 、 环戊二烯 在 二氯乙基铝 作用下， 生成 (1SR,2RS,7SR,8RS)-4-oxatricyclo[6.2.1.0^2,7]undec-8-en-3-one
  参考文献：
  名称：

  Reductive, radical-induced cyclization of 5-hexenals as a biomimetic model of the chemistry of secologanin formation

  摘要：

  DOI：

  10.1021/jo00225a042

文献信息

• Experimental and Computational Investigations of the Reactions between α,β‐Unsaturated Lactones and 1,3‐Dienes by Cooperative Lewis Acid/Brønsted Acid Catalysis
  作者：Anja Weber、Martin Breugst、Jörg Pietruszka

  DOI：10.1002/ange.202008365

  日期：2020.10.12

  AbstractThe reactions of α,β‐unsaturated δ‐lactones with activated dienes such as 1,3‐dimethoxy‐1‐[(trimethylsilyl)oxy]‐1,3‐butadiene (Brassard's diene) are barely known in literature and show high potential for the synthesis of isocoumarin moieties. An in‐depth investigation of this reaction proved a stepwise mechanism via the vinylogous Michael‐products. Subsequent cyclisation and oxidation by LHMDS

  摘要α,β-不饱和δ-内酯与活化二烯如1,3-二甲氧基-1-[(三甲基硅基)氧基]-1,3-丁二烯（布拉萨二烯）的反应在文献中鲜为人知，并且显示出很高的潜力异香豆素部分的合成。对该反应的深入研究证明了通过插烯迈克尔产物的逐步机制。随后通过 LHMDS 和 DDQ 进行环化和氧化，通过三个步骤分别提供了六种 Mellein 衍生物 (30-84%) 和四种当归碱衍生物 (40-78%)。DFT 计算提供了对反应机理的深入了解并支持逐步反应理论。
• Dimethylaluminum methide complex Tf2CHAlMe2: an effective catalyst for Diels–Alder reaction of α,β-unsaturated lactone derivatives with cyclopentadiene
  作者：Hikaru Yanai、Arata Takahashi、Takeo Taguchi

  DOI：10.1016/j.tet.2007.09.061

  日期：2007.12

  catalyst system for the catalytic DA reaction of less reactive α,β-unsaturated lactone derivative with cyclopentadiene (CP). In this catalyst system, Tf2CHAlMe2 is an active species and an excess amount of Me3Al plays an important role to lower the catalyst loading. Substituent effect of the lactone framework on π-facial selectivity was also examined. In the reactions of both γ-substituted 5-membered lactone

  发现通过将Tf 2 CH 2和Me 3 Al混合而获得的路易斯酸是反应性较低的α，β-不饱和内酯衍生物与环戊二烯（CP）的催化DA反应的有效催化剂体系。在该催化剂体系中，Tf 2 CHAlMe 2是活性物质，过量的Me 3 Al在降低催化剂负载量方面起着重要作用。还研究了内酯骨架对π面选择性的取代作用。在γ取代的5元内酯衍生物和γ或δ甲基化的6元内酯衍生物与CP的反应中，对抗观察到γ-或δ-取代基的表面。另一方面，在γ-或γ-甲基化的7元内酯衍生物的情况下，CP有利地侵蚀了合成面上。
• Solution-phase ring opening cross-metathesis of bicyclic alkenes with styrene derivatives and its application to “resin capture” solid-phase synthesis
  作者：Gregory D. Cuny、Jingrong Cao、Alban Sidhu、James R. Hauske

  DOI：10.1016/s0040-4020(99)00298-7

  日期：1999.7

  The solution-phase ring opening cross-metathesis (ROM) of bicyclic alkenes with styrene derivatives is described. The influence of bicyclic alkene substituents on the rate and product distribution of solution-phase ROM reactions with styrene derivatives is discussed. In addition, a method for the "resin capture" of solution-phase ROM products by resin-bound amines is also illustrated. (C) 1999 Elsevier Science Ltd. All rights reserved.
• Bis-aluminated triflic amide promoted Diels–Alder reactions of α,β-unsaturated lactones
  作者：Akio Saito、Hikaru Yanai、Takeo Taguchi

  DOI：10.1016/j.tetlet.2004.10.079

  日期：2004.12

  The bis-aluminated triflic amides such as TfN[Al(Me)Cl](2) and TfN[Al(iBU)(2)](2,) which are derived from triffic amide (I mol) and aluminum reagent (2 mol), can efficiently promote the Diels-Alder reaction of alpha, beta-unsaturated lactone derivatives as dienophiles. Selection of the ligand on aluminum of these Lewis acids should be important depending on the combination of dienophile and 1,3-diene. (C) 2004 Elsevier Ltd. All rights reserved.