α-Phenyl-N-m-chlorophenylnitron | 32019-34-4

• 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: α-Phenyl-N-m-chlorophenylnitron
• 英文别名: N-[3-chlorophenyl]-α-phenyl nitrone；phenyl-N-3-chlorophenyl nitrone；N-(3-chlorophenyl)-1-phenylmethanimine oxide
• CAS: 32019-34-4
• 化学式: C₁₃H₁₀ClNO
• 分子量: 231.681
• InChiKey: ZHXJVVRBKITVLS-UHFFFAOYSA-N

物化性质

• 沸点：
  389.7±44.0 °C(Predicted)
• 密度：
  1.253±0.06 g/cm3(Predicted)

计算性质

• 辛醇/水分配系数(LogP)：
  2.5
• 重原子数：
  16
• 可旋转键数：
  2
• 环数：
  2.0
• sp3杂化的碳原子比例：
  0.0
• 拓扑面积：
  28.8
• 氢给体数：
  0
• 氢受体数：
  1

反应信息

• 作为反应物：
  描述：

  α-Phenyl-N-m-chlorophenylnitron 在 sodium tetrahydroborate 、 三乙胺 作用下， 以 甲醇 、 乙醚 为溶剂， 反应 9.0h， 生成 3-benzyl-5-chloro-1,3-benzoxazol-2(3H)-one
  参考文献：
  名称：

  Synthesis of 3-Alkylbenzoxazolones from N-Alkyl-N-arylhydroxylamines by Contiguous O-Trichloroacetylation, Trichloroacetoxy ortho-Shift, and Cyclization Sequence

  摘要：

  Benzoxazolone pharmacophore is present in clinical pharmaceuticals, drug candidates, and many compounds having a wide spectrum of biological activities. The methods available for the synthesis of benzoxazolones have limited diversity due to problems in accessibility and air-sensitivity of diversely substituted o-aminophenols from which they are generally prepared by cyclocarbonylation with phosgene or its equivalents. The present paper describes a mild method for the synthesis of 3-alkylbenzoxazolones from easily accessible and air-stable nitroarenes. Nitroarenes were converted to N-alkyl-N-arylhydroxylamines in two steps involving partial reduction to arylhydroxylamines followed by selective N-alkylation. Treatment of N-alkyl-N-arylhydroxylamines with trichloroacetyl chloride and triethylamine afforded 3-alkylbenzoxazolones generally in good yields through an uninterrupted three-step sequence involving O-trichloroacetylation, N -> C-ortho trichloroacetoxy shift, and cyclization in a single pot at ambient temperatures. The present method is mild, wide in scope, economical, and regioselective. Many sensitive groups like alkyl and aryl esters, amide, cyano, and the carbon-carbon double bond survive the reaction.

  DOI：

  10.1021/jo401985h
• 作为产物：
  描述：

  3-硝基氯苯 、 苯甲醛 在 氯化铵 、 锌 作用下， 以 乙醇 、 水 为溶剂， 反应 12.0h， 生成 α-Phenyl-N-m-chlorophenylnitron
  参考文献：
  名称：

  手性N，N'-二氧化物/ Co（II）促进亚硝基与亚甲基吲哚酮的不对称1,3-偶极环加成反应

  摘要：

  已开发出一种手性N，N'-二氧化物/ Co（BF4）2•6H2O络合物催化体系，可有效催化亚硝基吲哚酮与亚硝基吲哚酮类化合物的不对称1,3-偶极环加成反应。相应的具有三个连续的季-三级立体中心的手性多取代的螺异异唑烷类化合物以中等至高产率获得，具有优异的dr和ee值（高达97％的产率，> 19：1 dr和98％的ee）。

  DOI：

  10.1039/c7cc03575f

文献信息

• Iron-Catalyzed Cyclization of Nitrones with Geminal-Substituted Vinyl Acetates: A Direct [4 + 2] Assembly Strategy Leading to 2,4-Disubstituted Quinolines
  作者：Mingbing Zhong、Song Sun、Jiang Cheng、Ying Shao

  DOI：10.1021/acs.joc.6b01910

  日期：2016.11.18

  An iron-catalyzed intermolecular [4 + 2] cyclization of arylnitrones with geminal-substituted vinyl acetates was developed for the synthesis of 2,4-disubstituted quinolines in moderate to good yields with good functional group compatibilities. Preliminary mechanistic studies suggest a plausible iron-catalyzed C–H activation process under external-oxidant-free conditions.

  已开发了铁的芳基硝基酮与双取代的乙酸乙烯酯的铁催化的分子间[4 + 2]环化反应，用于合成2,4-二取代的喹啉，产率中等至良好，且具有良好的官能团相容性。初步的机理研究表明，在无外部氧化剂的条件下，铁催化的CH活化过程似乎是合理的。
• Rh(III)-Catalyzed C–H Cyclization of Arylnitrones with Diazo Compounds: Access to 3-Carboxylate Substituted<i>N</i>-Hydroxyindoles
  作者：Yazhou Li、Jian Li、Xiaowei Wu、Yu Zhou、Hong Liu

  DOI：10.1021/acs.joc.7b01393

  日期：2017.9.1

  Recently, N-hydroxyindole derivatives have received much interest because of their unique structural motif and various biological activities. In this study, we report the first example of a Rh(III)-catalyzed reaction of arylnitrones with α-diazoketoesters or α-diazodiketones to produce N-hydroxyindole derivatives. Intriguingly, we could build the N-hydroxyindole scaffold by blocking the cleavage of

  近来，N-羟基吲哚衍生物由于其独特的结构基序和各种生物活性而受到了广泛的关注。在这项研究中，我们报告的第一个例子是Rh（III）催化的芳基硝酮与α-二氮酮酸酯或α-二氮二酮生成N-羟基吲哚衍生物的反应。有趣的是，我们可以通过选择性地阻断N-O键的裂解来构建N-羟基吲哚骨架，同时优先消除α-二氮酮酸酯或α-二氮二酮的酰基。
• Rhodium(III)‐Catalyzed Asymmetric Access to Spirocycles through C−H Activation and Axial‐to‐Central Chirality Transfer
  作者：Lingheng Kong、Xi Han、Song Liu、Yun Zou、Yu Lan、Xingwei Li

  DOI：10.1002/anie.202000174

  日期：2020.4.27

  Axial-to-central chirality transfer is an important strategy to construct chiral centers, where the axially chiral reagents are mostly limited to atropomerically stable ones. Reported herein is a RhIII -catalyzed enantioselective spiroannulative synthesis of nitrones. The coupling proceeds via C-H arylation to give an atropomerically metastable biaryl, followed by intramolecular dearomative trapping

  轴向向中心手性转移是构建手性中心的重要策略，其中轴向手性试剂主要限于阻转稳定剂。本文报道了RhIII催化的硝酮的对映选择性螺环合成。偶联通过CH芳基化进行，得到阻转异构的亚稳联芳基，然后在具有高度手性转移的氧化条件下进行分子内脱芳香化捕集。
• Gold‐Catalyzed Oxidative Aminocyclizations of Propargyl Alcohols and Propargyl Amines to Form Two Distinct Azacyclic Products: Carbene Formation versus a 3,3‐Sigmatropic Shift of an Initial Intermediate
  作者：Amit Vijay Sasane、Antony Sekar Kulandai Raj、Tzu‐Hsuan Chao、Mu‐Jeng Chen、Rai‐Shung Liu

  DOI：10.1002/chem.202003840

  日期：2020.12.15

  Gold‐catalyzed oxidations of propargyl alcohols with nitrones by using a P(tBu)2(o‐biphenyl)Au+ catalyst, afforded bicyclic annulation products from the Mannich reactions of gold enolates. The same reactions of propargyl amines with nitrones by using the same gold catalyst gave distinct oxoarylation products. Our DFT calculations indicate that oxidation of propargyl alcohols with nitrones by using electron‐rich

  通过使用P（t Bu）2（邻联苯）Au +催化剂在金催化下用炔烃氧化炔丙醇，从烯醇金的曼尼希反应中得到双环环化产物。通过使用相同的金催化剂，炔丙基胺与硝酮的相同反应产生不同的羰基化产物。我们的DFT计算表明，通过使用富电子的金催化剂将炔丙醇与硝酮氧化仅会生成金卡宾，这些碳卡宾可以生成烯醇盐类金的烯醇盐或羰基化中间体，而烯醇盐类的阻挡层小于羰基化物种。
• Chemoselective CC Bond Cleavage of Epoxide Motifs: Gold(I)-Catalyzed Diastereoselective [4+3] Cycloadditions of 1-(1-Alkynyl)oxiranyl Ketones and Nitrones
  作者：Tao Wang、Junliang Zhang

  DOI：10.1002/chem.201002395

  日期：2011.1.3

  Cutting carbon! A novel facile strategy for the CC bond cleavage of oxiranyl ketones has been developed. Carbophilic gold(I) activation of the alkyne side chain mediates a heterocyclization and subsequent CC bond cleavage (see scheme).

  减碳！已开发出一种新的简便方法，可用于氧化奥氮基酮的CC键断裂。炔侧链的嗜碳金（I）活化介导杂环化和随后的CC键裂解（请参阅方案）。