tert-butyl 3-methyl-2H-azirine-2-carboxylate | 847776-99-2

• 分子结构分类: 有机化合物 - 有机酸及其衍生物 - 羧酸及其衍生物
• 英文名称: tert-butyl 3-methyl-2H-azirine-2-carboxylate
• CAS: 847776-99-2
• 化学式: C₈H₁₃NO₂
• 分子量: 155.197
• InChiKey: XLFZUZQHSNWDET-UHFFFAOYSA-N

物化性质

• 沸点：
  192.0±50.0 °C(Predicted)
• 密度：
  1.08±0.1 g/cm3(Predicted)

计算性质

• 辛醇/水分配系数(LogP)：
  1
• 重原子数：
  11
• 可旋转键数：
  3
• 环数：
  1.0
• sp3杂化的碳原子比例：
  0.75
• 拓扑面积：
  38.7
• 氢给体数：
  0
• 氢受体数：
  3

反应信息

• 作为反应物：
  描述：

  tert-butyl 3-methyl-2H-azirine-2-carboxylate 在 RuCl2(1,3-dimesityl-imidazolidin-2-yl)(PCy3)(=CHPh) 、 platinum(IV) oxide 、 氢气 、 N,N-二异丙基乙胺 作用下， 以 四氢呋喃 、 二氯甲烷 、 乙酸乙酯 为溶剂， 65.0 ℃ 、101.33 kPa 条件下， 反应 9.0h， 生成
  参考文献：
  名称：

  通过逐步环化/开环序列从2 H-叠氮基合成高度取代的氮杂酮

  摘要：

  具有2个H-叠氮基的逐步环化序列由非对映选择性烯丙基化，N-酰化和一个闭环易位构筑，由两个H-叠氮基制备具有1-氮杂双环[4.1.0]庚-2-基的双环氮丙啶。环。烯烃氢化或官能化后，将所得氮杂双环化合物与羧酸（或硫亲核试剂）进行区域选择性开环，得到具有氮原子的α和β位置具有酯部分或三氟甲基基团和四取代碳原子的高度取代的氮杂酮。 ， 分别。

  DOI：

  10.1021/acs.orglett.9b00999
• 作为产物：
  描述：

  tert-butyl (3E)-3-(4-methylphenyl)sulfonyloxyiminobutanoate 在 三乙胺 作用下， 反应 6.5h， 以66%的产率得到tert-butyl 3-methyl-2H-azirine-2-carboxylate
  参考文献：
  名称：

  Lipase-Catalyzed Resolution of (2R*,3S*)- and (2R*,3R*)-3-Methyl-3-phenyl-2-aziridinemethanol at Low Temperatures and Determination of the Absolute Configurations of the Four Stereoisomers

  摘要：

  Lipase-catalyzed resolution of (2R*,3S*)-3-methyl-3-phenyl-2-aziridinemethanol, (+/-)-2, at low temperatures gave synthetically useful (2R,3S)-2 and its acetate (2S,3R)-2a with (2S)-selectivity (E = 55 at -40degreesC), while a similar reaction of (2R*,3R*)-3-methyl-3-phenyl-2-aziridinemethanol, (+/-)-3, gave (2S,3S)-3 and its acetate (2R,3R)-3a with (2R)-selectivity (E = 73 at -20degreesC). Compound (+/-)-2 was prepared conveniently via diastereoselective addition of MeMgBr to tert-butyl 3-phenyl2H-azirine-2-carboxylate, (+/-)-1a, which was successfully prepared by the Neber reaction of oxime tosylate of tert-butyl benzoyl acetate 7a. The tert-butyl ester was requisite to promote this reaction. For determination of the absolute configuration of (2S,3R)-2a, enantiopure (2S,3R)-2 was independently prepared in three steps involving diastereoselective methylation of 3-phenyl-2H-azirine-2-methanol, (S)-10, with MeMgBr. The absolute configuration of (2S,3S)-3 was determined by X-ray analysis of the corresponding N-(S)-2-(6-methoxy-2-naphthyl)propanoyl derivative (S,S,S)-13.

  DOI：

  10.1021/jo048243n

文献信息

• Rh^II-Catalyzed [3+2] Cycloaddition of 2 <i>H</i>-Azirines with<i>N</i>-Sulfonyl-1,2,3-Triazoles
  作者：Yun-Zhou Zhao、Hai-Bin Yang、Xiang-Ying Tang、Min Shi

  DOI：10.1002/chem.201406460

  日期：2015.2.23

  RhII‐catalyzed intermolecular [3+2] cycloaddition of 2 H‐azirines with N‐sulfonyl‐1,2,3‐triazoles is disclosed, in which a series of fully functionalized pyrroles is produced via rhodium azavinyl carbene intermediates. A distinct feature of this reaction is that the azavinyl carbene serves as a [2 C] equivalent, instead of as [1 C] or aza‐[3 C] synthons, which have been reported previously in cyclopropanations

  Rh II催化的2 H-叠氮基与N-磺酰基-1,2,3-三唑的分子间[3 + 2]环加成反应 ，其中通过氮杂乙烯基卡宾铑中间体生产了一系列功能完全的吡咯。该反应的显着特征是，氮杂乙烯基卡宾可作为[2 C]等效物，而不是先前在环丙烷和[3+ n ]环加成中报道的[1 C]或aza- [3 C]合成子。。此外，该方法学也已成功应用于URB447的全合成以及阿托伐他汀（立普妥）的正式合成。
• Lewis Acid-Catalyzed Diastereoselective Synthesis of Multisubstituted <i>N</i>-Acylaziridine-2-carboxamides from 2<i>H</i>-Azirines via Joullié–Ugi Three-Component Reaction
  作者：Anikó Angyal、András Demjén、Edit Wéber、Anita K. Kovács、János Wölfling、László G. Puskás、Iván Kanizsai

  DOI：10.1021/acs.joc.7b03189

  日期：2018.4.6

  A ZnCl2-catalyzed diastereoselective Joullié–Ugi three-component reaction from 2H-azirines, isocyanides, and carboxylic acids was established. The protocol allows the preparation of highly and diversely functionalized N-acylaziridine-2-carboxamide derivatives in up to 82% isolated yields. Moreover, the applicability of N-acylaziridines is demonstrated through a variety of transformations.

  建立了由2 H-叠氮基，异氰酸酯和羧酸组成的ZnCl 2催化的非对映选择性Joullié-Ugi三组分反应。该方案允许以高达82％的分离产率制备高度多样化的功能化N-酰基氮丙啶-2-羧酰胺衍生物。而且，通过各种转化证明了N-酰基氮丙啶的适用性。
• 1,3-Dipolar Cycloaddition of Isatin-Derived Azomethine Ylides with 2<i>H</i>-Azirines: Stereoselective Synthesis of 1,3-Diazaspiro[bicyclo[3.1.0]hexane]oxindoles
  作者：Anikó Angyal、András Demjén、Veronika Harmat、János Wölfling、László G. Puskás、Iván Kanizsai

  DOI：10.1021/acs.joc.9b00242

  日期：2019.4.5

  A regio- and diastereoselective 1,3-dipolar cycloaddition of 2H-azirines with azomethine ylides generated in situ from isatins and α-amino acids has been elaborated, affording an unprecedented aziridine-fused spiro[imidazolidine-4,3′-oxindole] framework. This one-pot three-component reaction tolerates a wide range of substrates and enables the construction of highly diverse 1,3-diazaspiro[bicyclo[3

  精心设计了2 H-叠氮基与区域的非对映体和非对映体选择性1,3-偶极环加成反应，该叠氮化物是从靛红和α-氨基酸原位生成的，其提供了前所未有的氮丙啶融合螺[imidazolidine-4,3'-oxindole]框架。这种一锅三组分反应可耐受多种底物，并能在温和条件下以高达81％的分离产率构建高度多样化的1,3-二氮杂螺并[双环[3.1.0]己烷]吲哚。
• Regioselective Synthesis of Indolopyrazines through a Sequential Rhodium-Catalyzed Formal [3+3] Cycloaddition and Aromatization Reaction of Diazoindolinimines with Azirines
  作者：Yonghyeon Baek、Chanyoung Maeng、Hyunseok Kim、Phil Ho Lee

  DOI：10.1021/acs.joc.8b00115

  日期：2018.2.16

  A regioselective synthetic method for the preparation of indolopyrazines was demonstrated through a sequential Rh-catalyzed formal [3+3] cycloaddition and aromatization reaction of a wide range of diazoindolinimines with azirines. Because the previously reported synthetic methods afforded mixtures of indolopyrazines, the present method using unsymmetrical azirines has a strong advantage from a regioselectivity

  通过连续的Rh催化的正式[3 + 3]环加成反应以及各种重氮吲哚并咪唑与叠氮基的芳构化反应，证明了制备吲哚并吡嗪的区域选择性合成方法。因为先前报道的合成方法提供了吲哚并吡嗪的混合物，所以从区域选择性的角度来看，使用不对称叠氮基的本方法具有很强的优势。
• Acid-Catalyzed 1,3-Dipolar Cycloaddition of 2<i>H</i>-Azirines with Nitrones: An Unexpected Access to 1,2,4,5-Tetrasubstituted Imidazoles
  作者：Anikó Angyal、András Demjén、János Wölfling、László G. Puskás、Iván Kanizsai

  DOI：10.1021/acs.joc.9b03288

  日期：2020.3.6

  The first 1,3-dipolar cycloaddition of 2H-azirines with nitrones, a straightforward approach toward the regioselective synthesis of 1,2,4,5-tetrasubstituted imidazoles, is reported. This trifluoroacetic acid-catalyzed protocol tolerates a broad range of aliphatic and aromatic substrates, offering an efficient access to highly diverse, multisubstituted imidazoles in isolated yields up to 83% under mild

  据报道，2H-叠氮基与硝酮的第一个1,3-偶极环加成反应是对1,2,4,5-四取代的咪唑进行区域选择性合成的直接方法。该三氟乙酸催化的方案可耐受多种脂族和芳族底物，在温和条件下，分离出的收率高达83％，可高效获得高度多样化的多取代咪唑。