3-(m-tolyl)-2H-azirine | 187795-63-7

• 分子结构分类: 有机化合物 - 有机杂环化合物 - 叠氮烷
• 英文名称: 3-(m-tolyl)-2H-azirine
• 英文别名: 3-(3-Methylphenyl)-2H-azirene；3-(3-methylphenyl)-2H-azirine
• CAS: 187795-63-7
• 化学式: C₉H₉N
• 分子量: 131.177
• InChiKey: ITJKAVYNAFEJTH-UHFFFAOYSA-N

物化性质

• 沸点：
  220.7±33.0 °C(Predicted)
• 密度：
  1.05±0.1 g/cm3(Predicted)

计算性质

• 辛醇/水分配系数(LogP)：
  1.9
• 重原子数：
  10
• 可旋转键数：
  1
• 环数：
  2.0
• sp3杂化的碳原子比例：
  0.22
• 拓扑面积：
  12.4
• 氢给体数：
  0
• 氢受体数：
  1

反应信息

• 作为反应物：
  描述：

  碘苯二乙酸 、 3-(m-tolyl)-2H-azirine 在 iron(II) diacetylacetonate 作用下， 以 甲苯 为溶剂， 反应 8.0h， 以80%的产率得到3-(m-tolyl)-2H-azirin-2-yl acetate
  参考文献：
  名称：

  Iron-Catalyzed C(sp³)–H Acyloxylation of Aryl-2H Azirines with Hypervalent Iodine(III) Reagents

  摘要：

  This letter describes an iron-catalyzed C(sp(3))-H acyloxylation of aryl-2H azirines with hypervalent iodine(III) reagents (HIRs) serving as both an oxidant and a reagent. This methodology provides a rapid access to a wide range of monoacyloxylated 3-aryl-2H-azirines in moderate to good yields.

  DOI：

  10.1021/acs.orglett.8b00442
• 作为产物：
  描述：

  1,2-二溴-1-(3-甲基苯基)乙烷 在 sodium azide 、 sodium hydroxide 作用下， 以 水 、 二甲基亚砜 、 甲苯 为溶剂， 反应 41.0h， 生成 3-(m-tolyl)-2H-azirine
  参考文献：
  名称：

  Visible-Light Photoredox Catalyzed Three-Component Cyclization of 2H-Azirines, Alkynyl Bromides, and Molecular Oxygen to Oxazole Skeleton

  摘要：

  A novel three-component cyclization of 2H-azirines, alkynyl bromides, and molecular oxygen under visible light photoredox catalysis at room temperature has been developed, which provides a direct approach to a wide range of substituted oxazoles in moderate to good yields.

  DOI：

  10.1021/acs.orglett.6b01696

文献信息

• Self-Catalyzed Rapid Synthesis of <i>N</i>-Acylated/<i>N</i>-Formylated α-Aminoketones and <i>N</i>-Hydroxymethylated Formamides from 3-Aryl-2<i>H</i>-Azirines and 2-Me/Ph-3-Aryl-2<i>H</i>-Azirines
  作者：Aramita De、Sougata Santra、Grigory V. Zyryanov、Adinath Majee

  DOI：10.1021/acs.orglett.0c01206

  日期：2020.5.15

  by the reaction of 3-aryl-2H-azirines and highly substituted 2-Me/Ph-3-aryl-2H-azirines with various carboxylic acids under ambient air within 10 min at room temperature. N-Trifluoroacetylated α-aminoketones with different substituents have been reported in the presence of trifluoroacetic acid. This protocol is equally effective to synthesize N-formylated α-aminoketone and N-hydroxymethylated formamide

  通过3-芳基-2H-叠氮基和高度取代的2-Me / Ph-3-芳基-2H-叠氮基与各种羧酸的反应，已经建立了一种快速有效的合成N-酰化α-氨基酮衍生物的方法。在室温下10分钟内在环境空气中。已经报道了在三氟乙酸存在下具有不同取代基的N-三氟乙酰化的α-氨基酮。该方案对于合成N-甲酰化的α-氨基酮和N-羟甲基化的甲酰胺衍生物同样有效。
• Copper-Catalyzed Ring-Expansion Cascade of Azirines with Alkynes: Synthesis of Multisubstituted Pyridines at Room Temperature
  作者：Chandragiri Sujatha、Chandra Shekar Bhatt、Mahesh Kumar Ravva、Anil K. Suresh、Kayambu Namitharan

  DOI：10.1021/acs.orglett.8b01090

  日期：2018.6.1

  the synthesis of pyridines, enabled by a copper/triethylamine catalytic system via simultaneous generation and utilization of yne-enamine and skipped-yne-imine intermediates, is reported. Experimental as well as computational mechanistic studies revealed that the role of triethylamine is crucial in deciding the reaction pathway toward the pyridine products. This process offers a novel, one-step, direct

  据报道，由铜/三乙胺催化系统通过同时生成和利用炔-烯胺和跳过的炔-亚胺中间体而实现的，第一个氮杂环丙烷与炔烃的分子间扩环级联反应用于合成吡啶。实验和计算机理研究表明，三乙胺的作用对于决定向吡啶产物的反应途径至关重要。此过程提供了一种新颖的，一步一步，直接且实用的策略，可在极其温和的条件下快速构建高度取代的吡啶，并具有已安装的炔烃功能。
• Catalytic Enantioselective Aza-Benzoin Reactions of Aldehydes with 2<i>H</i> -Azirines
  作者：Qiupeng Peng、Donghui Guo、Jianbo Bie、Jian Wang

  DOI：10.1002/anie.201712785

  日期：2018.3.26

  The unprecedented enantioselective aza‐benzoin reaction of aldehydes with 2H‐azirines was developed by utilizing a chiral N‐heterocyclic carbene as the catalyst. A wide range of corresponding aziridines can be obtained in good yields with high enantioselectivities. The obtained optically active aziridines should be useful in the synthesis of other valuable molecules.

  醛与2 H-叠氮基的醛的对映选择性氮杂安息香反应是前所未有的，它是利用手性N-杂环卡宾作为催化剂而开发的。可以以高收率和高对映选择性获得各种相应的氮丙啶。所获得的旋光氮丙啶应用于合成其他有价值的分子。
• Enantioselective Reaction of 2<i>H</i> -Azirines with Phosphite Using Chiral Bis(imidazoline)/Zinc(II) Catalysts
  作者：Shuichi Nakamura、Daiki Hayama

  DOI：10.1002/anie.201704133

  日期：2017.7.17

  The first highly enantioselective nucleophilic addition reaction of phosphites with 2H‐azirines has been developed. The reaction was applied to various 3‐substituted 2H‐azirines using novel chiral bis(imidazoline)/ZnII catalysts to afford products in good yield with high enantioselectivity. The transformation of the obtained optically active aziridines showed that 2H‐azirines act as either α,β‐ or

  已经开发了第一个亚磷酸酯与2 H-叠氮基的高对映选择性亲核加成反应。使用新型手性双（咪唑啉）/ Zn II催化剂，将该反应应用于各种3-取代2 H-叠氮基，以高收率和高对映选择性提供产物。所获得的光学活性氮丙啶的转化表明，2个H-叠氮基充当α，β-或β，β-二碳代氨基胺合成子。
• Selective C–C bond formation from rhodium-catalyzed C–H activation reaction of 2-arylpyridines with 3-aryl-2<i>H</i>-azirines
  作者：Yonghyeon Baek、Jinwoo Kim、Hyunseok Kim Hyunseok Kim、Seung Jin Jung、Ho Ryu、Suyeon Kim、Jeong-Yu Son、Kyusik Um、Sang Hoon Han、Hyung Jin Seo、Juyoung Heo、Kooyeon Lee、Mu-Hyun Baik、Phil Ho Lee

  DOI：10.1039/c8sc05142a

  日期：——

  coupling. Computational studies quickly revealed and prototype experimental work confirmed that neither the formation of the expected metal nitrene complexes nor the C–N coupling were viable. Instead, azirine ring-opening followed by C–C coupling was found to be much more favorable to give imines that readily underwent hydrolysis in aqueous conditions to form acylmethyl-substituted products. This new method

  通过探索使用DFT计算的原型反应并在计算机制的指导下进行有针对性的实验，开发了一种使用3-芳基-2 H-叠氮基合成酰基甲基取代的2-芳基吡啶衍生物的新方法。2小时最初假设-Azirine在金属中心开环，以提供可能经历C–N偶联的熟悉的金属腈络合物。计算研究迅速揭示，原型实验工作证实，形成预期的金属氮配合物和C–N偶联均不可行。取而代之的是，发现将叠氮基开环然后进行C-C偶联更有利于生成在水性条件下易于水解以形成酰基甲基取代产物的亚胺。这种新方法用途广泛，对具有高官能团耐受性的多种底物具有选择性。通过方便地一锅合成生物相关的杂环（例如吡啶并异吲哚和吡啶并异喹啉酮）证明了该新方法的实用性。