N-allyl-N-(toluene-4-sulfonyl)-2-aminoacetaldehyde oxime | 873692-52-5

• 分子结构分类: 有机化合物 - 苯类化合物 - 苯和取代衍生物
• 英文名称: N-allyl-N-(toluene-4-sulfonyl)-2-aminoacetaldehyde oxime
• 英文别名: N-allyl-N-tosyl-2-aminoacetaldehydeoxime；N-(2-hydroxyiminoethyl)-4-methyl-N-prop-2-enylbenzenesulfonamide
• CAS: 873692-52-5
• 化学式: C₁₂H₁₆N₂O₃S
• 分子量: 268.337
• InChiKey: YTTAEQUSQWZMCE-UHFFFAOYSA-N

物化性质

• 沸点：
  435.0±55.0 °C(Predicted)
• 密度：
  1.17±0.1 g/cm3(Predicted)

计算性质

• 辛醇/水分配系数(LogP)：
  1.9
• 重原子数：
  18
• 可旋转键数：
  6
• 环数：
  1.0
• sp3杂化的碳原子比例：
  0.25
• 拓扑面积：
  78.4
• 氢给体数：
  1
• 氢受体数：
  5

反应信息

• 作为反应物：
  描述：

  N-allyl-N-(toluene-4-sulfonyl)-2-aminoacetaldehyde oxime 在 咪唑 、 三氟化硼乙醚 作用下， 以 1,2-二氯乙烷 、 N,N-二甲基甲酰胺 为溶剂， 反应 40.0h， 生成 (1RS,5SR)-3-(toluene-4-sulfonyl)-3,7-diaza-6-oxabicyclo[3.2.1]octane
  参考文献：
  名称：

  Intramolecular Cycloaddition of O-tert-Butyldimethylsilyloximes in the Presence of BF₃·OEt₂

  摘要：

  Intramolecular cycloaddition of novel 1,3-dipoles, N-boranonitrones, was examined. Treatment of O-tert-butyldimethylsilyloximes 9-12 having olefin moieties with 2 equiv of BF3 center dot OEt2 generated N-boranonitrones, which underwent intramolecular cycloaddition to afford N-nonsubstituted cycloadducts 16 (and/or 18) after extractive workup. Despite the Lewis-acidic conditions, the olefin geometry of the substrates was retained in the cycloadducts in the present cycloaddition. The electronic nature of the N-boranonitrones appeared to be electrophilic. In the case of substrate 11c, having an electron-donating methyl group at an internal position of the olefin moiety, the cycloaddition gave the bridged cycloadduct 18b. The cycloaddition proceeded at relatively low temperature, and the diastereoselectivity was high.

  DOI：

  10.1021/jo051652e
• 作为产物：
  描述：

  N-allyl-4-methyl-N-(2-oxoethyl)benzenesulfonamide 在 盐酸羟胺 、 碳酸氢钠 作用下， 以 乙醇 、 水 为溶剂， 以613 mg的产率得到N-allyl-N-(toluene-4-sulfonyl)-2-aminoacetaldehyde oxime
  参考文献：
  名称：

  Intramolecular Cycloaddition of O-tert-Butyldimethylsilyloximes in the Presence of BF₃·OEt₂

  摘要：

  Intramolecular cycloaddition of novel 1,3-dipoles, N-boranonitrones, was examined. Treatment of O-tert-butyldimethylsilyloximes 9-12 having olefin moieties with 2 equiv of BF3 center dot OEt2 generated N-boranonitrones, which underwent intramolecular cycloaddition to afford N-nonsubstituted cycloadducts 16 (and/or 18) after extractive workup. Despite the Lewis-acidic conditions, the olefin geometry of the substrates was retained in the cycloadducts in the present cycloaddition. The electronic nature of the N-boranonitrones appeared to be electrophilic. In the case of substrate 11c, having an electron-donating methyl group at an internal position of the olefin moiety, the cycloaddition gave the bridged cycloadduct 18b. The cycloaddition proceeded at relatively low temperature, and the diastereoselectivity was high.

  DOI：

  10.1021/jo051652e

文献信息

• Thiocyanate radical mediated dehydration of aldoximes with visible light and air
  作者：Yong-Liang Ban、Jian-Ling Dai、Xiao-Ling Jin、Qing-Bao Zhang、Qiang Liu

  DOI：10.1039/c9cc05354a

  日期：——

  We developed a new means of activating aldoximes by an in situ generated thiocyanate radical from ammonium thiocyanate and molecular oxygen at room temperature. With a catalytic amount of organic dye aizenuranine as the photocatalyst, the dehydration of aldoximes proceeds smoothly under visible light irradiation, providing a simple to handle, excellent functional group tolerance, and metal-free protocol

  我们开发了一种通过在室温下从硫氰酸铵和分子氧中原位生成的硫氰酸根来活化醛肟的新方法。用催化量的有机染料壬酸鸟嘌呤作为光催化剂，醛肟的脱水在可见光照射下平稳进行，提供了简单的操作，优异的官能团耐受性和适用于多种腈的无金属方案。
• Synthesis of <i>N</i>‐Aryl Isoxazolidines by Photo‐Promoted <i>N</i>‐Selective Arylation of Oximes and Cyclization Using Hypervalent Iodine Reagents and Copper Catalyst
  作者：Kosaku Tanaka、Mayumi Yoshida、Ayaka Yamamoto、Yoshimitsu Hashimoto、Nobuyoshi Morita、Osamu Tamura

  DOI：10.1002/adsc.202300110

  日期：2023.5.12

  corresponding N-aryl isoxazolidines in 26–95% yields. This method offers a faster reaction rate, lower catalyst loading and broader substrate scope of oxime than similar nitrone syntheses employing Chan-Lam-Evans coupling. The reaction involves via a radical/single electron transfer (SET) pathway, and does not proceed in the absence of photoirradiation.

  肟导致光促进、铜催化的N-选择性芳基化与二芳基碘盐生成硝酮，硝酮又与烯烃发生分子内或分子间 1,3-偶极环化，得到N-芳基异恶唑烷。被富电子或缺电子基团取代的高价碘试剂以26-95% 的收率提供相应的N-芳基异恶唑烷。与采用 Chan-Lam-Evans 偶联的类似硝酮合成相比，该方法提供更快的反应速率、更低的催化剂负载和更广泛的肟底物范围。该反应涉及通过自由基/单电子转移 (SET) 途径，并且在没有光照射的情况下不会进行。
• Direct Generation of <i>N</i>‐Alkoxycarbonyl Nitrones from Oximes: Intramolecular Cycloaddition of Oximes Having Alkene Moieties
  作者：Hiroto Sagara、Yoshio Suzuki、Nobuyoshi Morita、Shintaro Ban、Kosaku Tanaka、Ayaka Yamamoto、Yoshimitsu Hashimoto、Osamu Tamura

  DOI：10.1002/adsc.202300793

  日期：2023.11.21

  δ,ϵ-Unsaturated oximes, on heating with O-alkyl S-(pyridin-2-yl)carbonothioates (PySCO2R) in refluxing toluene, undergo intramolecular cycloaddition to give N-alkoxycarbonylated multi-cyclic compounds. Mechanistic studies indicate that the reaction involves direct generation of N-alkoxycarbonyl nitrones followed by cycloaddition, instead of intramolecular oxime-olefin cycloaddition (IOOC) followed

  δ,ε-不饱和肟与O-烷基S- (吡啶-2-基)硫代碳酸酯(PySCO 2 R)在回流甲苯中加热，发生分子内环加成，得到N-烷氧基羰基化多环化合物。机理研究表明，该反应涉及直接生成N-烷氧基羰基硝酮，然后进行环加成，而不是分子内肟-烯烃环加成(10OC)，然后进行烷氧基羰基化。DFT计算表明肟与PySCO 2 R的N-烷氧基羰基化是协同反应。肟与手性烷氧基羰基化试剂的反应表现出相当高的非对映面选择性。