3-acetyl-2-oxa-3-azabicyclo[2.2.1]hept-5-ene | 78607-56-4

• 分子结构分类: 有机化合物 - 有机杂环化合物 - 唑烷类
• 英文名称: 3-acetyl-2-oxa-3-azabicyclo[2.2.1]hept-5-ene
• 英文别名: 1-[(1R,4S)-2-oxa-3-azabicyclo[2.2.1]hept-5-en-3-yl]ethanone
• CAS: 78607-56-4
• 化学式: C₇H₉NO₂
• 分子量: 139.154
• InChiKey: GUDXSGDGGHLJMU-RQJHMYQMSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  0.2
• 重原子数：
  10
• 可旋转键数：
  0
• 环数：
  2.0
• sp3杂化的碳原子比例：
  0.57
• 拓扑面积：
  29.5
• 氢给体数：
  0
• 氢受体数：
  2

反应信息

• 作为反应物：
  描述：

  3-acetyl-2-oxa-3-azabicyclo[2.2.1]hept-5-ene 在 吡啶 、 甲醇 、 4-二甲氨基吡啶 、 sodium tetrahydroborate 、 sodium azide 、 hexacarbonyl molybdenum 、 electric eel acetylcholine esterase 、 potassium carbonate 作用下， 以 二氯甲烷 为溶剂， 生成 (-)-N-acetyl-4-aminocyclopent-2-enol
  参考文献：
  名称：

  Enzymatic Resolution of Aminocyclopentenols as Precursors to d- and l-Carbocyclic Nucleosides

  摘要：

  Racemic cis-4-aminocyclopent-2-en-1-ols were synthesized in three steps utilizing hetero Diels-Alder chemistry. Starting from suitably protected hydroxylamines, oxidization with sodium periodate and trapping with cyclopentadiene afforded cycloadducts (+/-)-5a-d. The N-O bond of the cycloadducts was reduced with Mo(CO)(6) to afford (+/-)-cis-4-aminocyclopent-2-en-1-ols (+/-)-6a-d. These compounds, or their corresponding acetates, were kinetically resolved by enzymatic acetylation or hydrolysis, respectively. Enzymatic acetylation of cis-N-(benzylcarbamoyl)-4-aminocyclopent-2-enol [(+/-)-6a] with Candida antarctica B lipase and Pseudomonas species lipase gave the corresponding acetate (-)-7a in 90% and 92% ee, respectively, after 40% conversion. Enzymatic hydrolysis of cis-N-acetyl-4-aminocyclopent-2-enol 1-O-acetate (+/-)-7d with electric eel acetylcholine esterase was successful in providing both cis-N-acetyl-4-aminocyclopent-2-enols (+)ed and (+)-7d in 92% ee (99% ee after a single recrystallization) after 40% conversion. Further synthetic transformations of these resolved synthetic building blocks and derivatives are also reported.

  DOI：

  10.1021/jo972265a
• 作为产物：
  描述：

  环戊二烯 在 碳酸氢钠 作用下， 以 吡啶 、 乙醚 、 乙醇 、 苯 为溶剂， 反应 5.0h， 生成 3-acetyl-2-oxa-3-azabicyclo[2.2.1]hept-5-ene
  参考文献：
  名称：

  2-氮杂-3-氧杂双环[2.2.1]庚烯盐酸盐的制备与转化

  摘要：

  1-氯-1-亚硝基环己烷与过量的新鲜制备的环戊二烯在乙醚：乙醇中的反应得到结晶的2-氮杂3氧杂双环（2.2.1）庚烯盐酸盐（1），产率为89％。用吡啶原位生成的2-氮杂3-氧杂双环（2.2.1）庚烯（2）可以被各种酰氯和酸酐酰化，从而提供了一种新颖且方便的途径来制备各种杂氮杂双环庚烯。由NaHCO 3在两相系统中生成的游离碱2易于与福尔马林反应，生成曼尼希碱加合物16，与PhNCS生成硫脲19，并与i-AmONO生成亚硝基化合物20。。在原位生成的2与过量的苯甲酰氯，MsCl和TsCl反应时，观察到PGG→PGE型裂解。令人惊讶地，在吡啶存在下1与ArCHO的反应产生具有高反应性卤素的N-α-氯芳基化合物。二酰亚胺的还原度为2时，母体的oxazabicycloheptane系统与PG-内过氧化物有关，后者的特征是盐酸盐或苯甲酰基衍生物。

  DOI：

  10.1016/s0040-4020(01)92440-8

文献信息

• A New Synthetic Route to Acylnitroso Intermediates and Their Applications in HDA and Ene Reactions
  作者：Ahmad Fakhruddin、Abdel-Moneim Abu-Elfotoh、Kazutaka Shibatomi、Seiji Iwasa

  DOI：10.2174/1570178614666170710101309

  日期：2018.2.7

  Diels-Alder (HDA) and ene reactions. Methods: Acylnitroso intermediates were readily obtained by hydrogen peroxide oxidation of hydroxamic acids catalyzed by Cu(I)-, Ir(I)- or Ru(II)-complexes and easily reacted with symmetric and asymmetric conjugated dienes beside their reaction with different alkenes which converted to biological active products. Results: The resulted acylnitroso intermediates were efficiently

  背景：酰基亚硝基中间体被认为是高反应性和有用的瞬态物质，已被用于合成多种生物活性化合物和合成药物。尽管有一些报道的产生这些中间体的方法，但是对于温和和环境良性的方案仍然存在挑战。本文中，我们报道了酰基亚硝基中间体的简便原位合成及其有效的杂Diels-Alder（HDA）和烯反应。 方法：酰基亚硝基中间体很容易通过Cu（I）-，Ir（I）-或Ru（II）-络合物催化的异羟肟酸的过氧化氢氧化而制得，并易于与对称和不对称共轭二烯反应，同时与不同的烯烃反应。转化为生物活性产品。 结果：在存在环戊二烯，环己二烯或α-萜品烯的情况下，以高收率有效地提供了所得酰基亚硝基中间体的杂Diels-Alder环加合物，并且对后者具有良好的区域选择性。在N-二烯基内酰胺的情况下，以完全的区域选择性，以高达89％的产率形成环加合物。在光学活性的N-二烯基焦谷氨酸盐的存在下，以高达72de的高产率形成非对映异构体。此
• Photocatalyzed Generation of Nitrosocarbonyl Intermediates Under Solar Light Irradiation
  作者：Teresa Basile、Luca Capaldo、Davide Ravelli、Paolo Quadrelli

  DOI：10.1002/ejoc.201900596

  日期：2020.3.15

  Tetrabutylammonium decatungstate (TBADT) promoted the oxidation of hydroxamic acids to nitrosocarbonyl intermediates. The reaction took place under aerobic conditions upon irradiation with solar light. The thus generated nitrosocarbonyls were efficiently trapped with reactive dienes to afford the corresponding Hetero Diels‐Alder (HDA) cycloadducts in good yields.

  四丁基癸酸铵（TBADT）促进了异羟肟酸氧化为亚硝基羰基中间体。在阳光照射下，该反应在有氧条件下进行。如此生成的亚硝基羰基化合物可有效地被反应性二烯捕获，从而以高收率获得相应的杂Diels-Alder（HDA）环加合物。
• Regio- and Stereoselective Ring Openings of 3-Aza-2-oxabicyclo[2.2.1]hept-5-ene Systems with Copper Catalyst-Modified Grignard Reagents:  Application to the Synthesis of an Inhibitor of 5-Lipoxygenase
  作者：Matthew D. Surman、Mark J. Mulvihill、Marvin J. Miller

  DOI：10.1021/jo016275u

  日期：2002.6.1

  hetero Diels-Alder cycloadducts 2 with organomagnesium reagents in the presence of a catalytic amount of copper induces ring opening to afford predominantly monocyclic anti-1,2-hydroxamic acids 12. Alkylmagnesium reagents were found to give superior regio- and stereoselectivities compared with vinyl and arylmagnesium reagents. This cycloadduct ring opening methodology was applied to the synthesis of a

  在催化量的铜存在下，用有机镁试剂处理酰基亚硝基杂Diels-Alder环加合物2导致开环，主要提供单环抗1,2-异羟肟酸12。发现烷基镁试剂相比于区域和立体选择性更好含乙烯基和芳基镁试剂。该环加合物开环方法学被用于合成基于独特的基于环戊烯基异羟肟酸的5-脂氧合酶抑制剂。
• Corrie, John E.T.; Kirby, Gordon W.; Mackinnon, John W.M., Journal of the Chemical Society. Perkin transactions I, 1985, p. 883 - 886
  作者：Corrie, John E.T.、Kirby, Gordon W.、Mackinnon, John W.M.

  DOI：——

  日期：——
• Straightforward hetero Diels–Alder reactions of nitroso dienophiles by microreactor technology
  作者：Jean-Christophe M.R. Monbaliu、Ana Cukalovic、Jacqueline Marchand-Brynaert、Christian V. Stevens

  DOI：10.1016/j.tetlet.2010.08.117

  日期：2010.11

  The hetero Diels-Alder reactions of 2-nitrosotoluene and some representative acylnitrosodienophiles with a selected set of 1,3-dienes were studied under microflow conditions. The main assets of the technology, that is, an accurate control of the reaction parameters and continuous operating, led to an increased efficiency of this reaction. (C) 2010 Elsevier Ltd. All rights reserved.