N-methyloxycarbonyl-2-aza-3-oxabicyclo[2.2.1]hept-5-ene | 70866-62-5

• 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: N-methyloxycarbonyl-2-aza-3-oxabicyclo[2.2.1]hept-5-ene
• 英文别名: Methyl 2-oxa-3-azabicyclo[2.2.1]hept-5-ene-3-carboxylate
• CAS: 70866-62-5
• 化学式: C₇H₉NO₃
• 分子量: 155.153
• InChiKey: VDESVFXGWBUXSQ-UHFFFAOYSA-N

物化性质

• 沸点：
  223.9±20.0 °C(Predicted)
• 密度：
  1.312±0.06 g/cm3(Predicted)

计算性质

• 辛醇/水分配系数(LogP)：
  0.6
• 重原子数：
  11
• 可旋转键数：
  1
• 环数：
  2.0
• sp3杂化的碳原子比例：
  0.57
• 拓扑面积：
  38.8
• 氢给体数：
  0
• 氢受体数：
  3

反应信息

• 作为反应物：
  描述：

  N-methyloxycarbonyl-2-aza-3-oxabicyclo[2.2.1]hept-5-ene 在 palladium on activated charcoal potassium permanganate 、 氢气 、 magnesium sulfate 、 对甲苯磺酸 作用下， 以 甲醇 、 水 为溶剂， 反应 26.5h， 生成
  参考文献：
  名称：

  2-Aza-3-oxabicyclo[2.2.1]heptene hydrochloride: An exceptionally versatile synthon for carbocyclic sugars and nucleosides

  摘要：

  The transformation of cyclopentadiene to 5'-desmethylene 1'-aza carbocyclic sugars has been achieved in four steps: 1. Cycloaddition of chloronitrosocyclohexane to 2-aza-3-oxabicyclo[2.2.1]heptene hydrochloride in EtOH-Et(2)O, 2. Nitrogen functionalization, 3. cis hydroxylation and 4. N-O bond cleavage. The protocols provided enable practical access to a range of 5'-desmethylene carbocyclic sugar analogs whose utility has been illustrated with synthesis of a novel 5'-desmethylene analog of aristeromycin. (C) 1997 Elsevier Science Ltd.

  DOI：

  10.1016/s0040-4020(97)00057-4
• 作为产物：
  描述：

  2-oxa-3-azabicyclo[2.2.1]hept-5-ene hydrochloride 、 氯甲酸甲酯 在 碳酸氢钠 作用下， 以 水 、 甲苯 为溶剂， 反应 24.0h， 以82%的产率得到N-methyloxycarbonyl-2-aza-3-oxabicyclo[2.2.1]hept-5-ene
  参考文献：
  名称：

  2-Aza-3-oxabicyclo[2.2.1]heptene hydrochloride: An exceptionally versatile synthon for carbocyclic sugars and nucleosides

  摘要：

  The transformation of cyclopentadiene to 5'-desmethylene 1'-aza carbocyclic sugars has been achieved in four steps: 1. Cycloaddition of chloronitrosocyclohexane to 2-aza-3-oxabicyclo[2.2.1]heptene hydrochloride in EtOH-Et(2)O, 2. Nitrogen functionalization, 3. cis hydroxylation and 4. N-O bond cleavage. The protocols provided enable practical access to a range of 5'-desmethylene carbocyclic sugar analogs whose utility has been illustrated with synthesis of a novel 5'-desmethylene analog of aristeromycin. (C) 1997 Elsevier Science Ltd.

  DOI：

  10.1016/s0040-4020(97)00057-4

文献信息

• Stereo- and Regioselectivity of Pd⁰/InI-Mediated Allylic Additions to Aldehydes and Ketones. <i>In Situ</i> Generation of Allylindium(III) Intermediates from <i>N</i>-Acylnitroso Diels−Alder Cycloadducts and 1-Amino-4-acetoxycyclopentenes
  作者：Wenlin Lee、Kyung-Hee Kim、Matthew D. Surman、Marvin J. Miller

  DOI：10.1021/jo026488z

  日期：2003.1.1

  and regiochemistry of their additions to aldehydes and ketones were investigated. Solvent, catalyst, and ionic effects were examined for the reaction of N-acetyl cycloadduct (11) and benzyloxyacetaldehyde (10). The solvent mixture of THF/H(2)O with Pd(OAc)(2).PPh(3) catalysis was found to be optimal. The addition of N-acetyl cycloadduct to aliphatic aldehydes afforded products in good yields and high

  酰基亚硝基Diels-Alder环加合物（11、37和45）和环戊烯基乙酸酯（8和9）衍生自钯（0）催化剂和碘化铟（I），以及立体异构体研究了它们向醛和酮中的添加的区域化学。检查了N-乙酰基环加合物（11）和苄氧基乙醛（10）反应的溶剂，催化剂和离子效应。发现THF / H（2）O与Pd（OAc）（2）.PPh（3）催化的混合溶剂是最佳的。将N-乙酰基环加合物添加到脂族醛中，以高收率和高区域和立体选择性提供产物，其中顺式1，4-异构体占产物的90-95％。与N-Boc（37a）和N-甲基氨基甲酸酯（37b）环加合物的反应也主要产生顺式1,4-产物。同样的区域选择性和立体选择性也适用于4-乙酰氧基-1-（N-羟基苯乙酰胺基）环戊烯的反应（8）。然而，4-乙酰氧基-1-苯基乙酰氨基环戊烯（9）仅提供反式-1,4-产物。描述了涉及螯合过渡态的机械推测。
• Synthesis and evaluation of 5-lipoxygenase translocation inhibitors from acylnitroso hetero-Diels–Alder cycloadducts
  作者：Joshua K. Bolger、Wen Tian、William R. Wolter、Wonhwa Cho、Mark A. Suckow、Marvin J. Miller

  DOI：10.1039/c0ob00714e

  日期：——

  Acylnitroso cycloadducts have proven to be valuable intermediates in the syntheses of a plethora of biologically active molecules. Recently, organometallic reagents were shown to open bicyclic acylnitroso cycloadducts and, more interestingly, the prospect of highly regioselective openings was raised. This transformation was employed in the synthesis of a compound with excellent inhibitory activity against 5-lipoxygenase ((±)-4a, IC50 51 nM), an important mediator of inflammation intimately involved in a number of disease states including asthma and cancer. Optimization of the copper-mediated organometallic ring opening reaction was accomplished allowing the further exploration of the biological activity. Synthesis of a number of derivatives with varying affinity for metal binding as well as pendant groups in a range of sizes was accomplished. Analogues were tested in a whole cell assay which revealed a subset of the compounds to be inhibitors of enzyme translocation, a mode of action not previously known and, potentially, extremely important for better understanding of the enzyme and inhibitor development. Additionally, the lead compound was tested in vivo in an established colon cancer model and showed very encouraging anti-tumorogenic properties.

  酰亚硝基环加合物已被证明是合成大量生物活性分子的有价值的中间体。最近，有机金属试剂被证明可以打开双环酰基亚硝基环加合物，更有趣的是，提出了高度区域选择性打开的前景。这种转化被用于合成一种对 5-脂氧合酶（(±)-4a，IC50 51 nM）具有优异抑制活性的化合物，5-脂氧合酶是一种重要的炎症介质，与包括哮喘和癌症在内的许多疾病状态密切相关。铜介导的有机金属开环反应的优化得以完成，从而可以进一步探索生物活性。合成了许多对金属结合具有不同亲和力以及各种尺寸的侧基的衍生物。在全细胞测定中对类似物进行了测试，结果显示化合物的一个子集是酶易位的抑制剂，这是一种以前未知的作用模式，并且对于更好地了解酶和抑制剂的开发可能极其重要。此外，先导化合物在已建立的结肠癌模型中进行了体内测试，并显示出非常令人鼓舞的抗肿瘤特性。
• Diaryl ether containing N-hydroxycarbamates from nitroso cycloadducts
  作者：Joshua Bolger、Marvin Miller

  DOI：10.1016/j.tetlet.2011.02.016

  日期：2011.4

  Regioselective ring opening of N-hydroxycarbamate-derived nitroso cycloadducts by a copper-catalyzed allylic alkylation reaction was achieved and applied to the synthesis of a set of substituted diaryl ether containing compounds. Use of protected 3-hydroxybenzyl bromide allowed access to a late stage phenol intermediate after protection of the N-hydroxy moiety that was generated from the ring opening reaction. The diaryl ethers were then formed by copper-mediated coupling with arylboronic acids. After selective deprotection, alumina-promoted transcarbamoylation provided the target compounds. Previous results indicate that the compounds may possess significant inhibitory potency against the proinflammatory enzyme 5-lipoxygenase. (C) 2011 Elsevier Ltd. All rights reserved.
• KECK G. E.; FLEMING S.; NICKELL D.; WEIDER P., SYNTH. COMMUN., 1979, 9, NO 4, 281-286
  作者：KECK G. E.、 FLEMING S.、 NICKELL D.、 WEIDER P.

  DOI：——

  日期：——
• 2-Aza-3-oxabicyclo[2.2.1]heptene hydrochloride: An exceptionally versatile synthon for carbocyclic sugars and nucleosides
  作者：Subramania Ranganathan、K.Shaji George

  DOI：10.1016/s0040-4020(97)00057-4

  日期：1997.3

  The transformation of cyclopentadiene to 5'-desmethylene 1'-aza carbocyclic sugars has been achieved in four steps: 1. Cycloaddition of chloronitrosocyclohexane to 2-aza-3-oxabicyclo[2.2.1]heptene hydrochloride in EtOH-Et(2)O, 2. Nitrogen functionalization, 3. cis hydroxylation and 4. N-O bond cleavage. The protocols provided enable practical access to a range of 5'-desmethylene carbocyclic sugar analogs whose utility has been illustrated with synthesis of a novel 5'-desmethylene analog of aristeromycin. (C) 1997 Elsevier Science Ltd.