tert-butyl 3-phenyl-2H-azirine-2-carboxylate | 847776-97-0

• 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-phenyl-2H-azirine-2-carboxylate
• 英文别名: t-Butyl 3-phenyl-2h-azirine-2-carboxylate
• CAS: 847776-97-0
• 化学式: C₁₃H₁₅NO₂
• 分子量: 217.268
• InChiKey: NDYFTIFHRQZCEF-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  2.7
• 重原子数：
  16
• 可旋转键数：
  4
• 环数：
  2.0
• sp3杂化的碳原子比例：
  0.38
• 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-phenyl-2H-azirine-2-carboxylate 在 lithium aluminium tetrahydride 作用下， 以 四氢呋喃 、 乙醚 为溶剂， 反应 9.5h， 生成 3-methyl-3-phenyl-2-aziridinemethanol
  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
• 作为产物：
  描述：

  5-氯-3-苯基恶唑 在 rhodium(II) pivalate 、 sodium hydride 作用下， 以 四氢呋喃 、 甲苯 为溶剂， 反应 21.0h， 生成 tert-butyl 3-phenyl-2H-azirine-2-carboxylate
  参考文献：
  名称：

  金属催化的5-杂原子取代的异恶唑的异构化为2-卤代-2H-叠氮基的新途径

  摘要：

  摘要 开发了一种方便的克级方法，该方法通过5-杂原子取代的4-卤代恶唑的金属催化异构化反应制备2-卤代-2 H-叠氮基-2-羧酸酯，硫代酸酯和酰胺。Rh 2（Piv）4可有效催化酯和酰胺的形成，而FeCl 2 ·4H 2 O是硫代酯合成的选择催化剂。此外，铑催化已成功地用于由非卤代的5-烷氧基异恶唑合成叠氮基-2-羧酸盐。 开发了一种方便的克级方法，该方法通过5-杂原子取代的4-卤代恶唑的金属催化异构化反应制备2-卤代-2 H-叠氮基-2-羧酸酯，硫代酸酯和酰胺。Rh 2（Piv）4可有效催化酯和酰胺的形成，而FeCl 2 ·4H 2 O是硫代酯合成的选择催化剂。此外，铑催化已成功地用于由非卤代的5-烷氧基异恶唑合成叠氮基-2-羧酸盐。

  DOI：

  10.1055/s-0036-1590822

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。
• Synthesis of Highly Substituted Azepanones from 2<i>H</i>-Azirines by a Stepwise Annulation/Ring-Opening Sequence
  作者：Alexandre Dupas、Pierre-Alexandre Lhotellier、Gérard Guillamot、Christophe Meyer、Janine Cossy

  DOI：10.1021/acs.orglett.9b00999

  日期：2019.5.17

  Bicyclic aziridines possessing a 1-azabicyclo[4.1.0]heptan-2-one core were prepared from 2H-azirines by a stepwise annulation sequence involving a diastereoselective allylindanation, an N-acylation, and a ring-closing metathesis to construct the six-membered ring. After hydrogenation or functionalization of the olefin, regioselective ring opening of the resulting azabicyclic compounds with carboxylic

  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。
• 2<i>H</i>-Azirines as Potential Bifunctional Chemical Linkers of Cysteine Residues in Bioconjugate Technology
  作者：Yang Chen、Wenjie Yang、Jiamin Wu、Wangbin Sun、Teck-Peng Loh、Yaojia Jiang

  DOI：10.1021/acs.orglett.0c00415

  日期：2020.3.6

  2H-Azirine-2-caboxamides have been designed to perform as a new type of bifunctional thiol linker under very mild reaction conditions. The cleavage of a C-N double bond of 2H-azirine furnishes an amino amide functional group in situ through a thiol addition and ring-opening process. It works with a broad scope of thiols and 2H-azirines in the absence of any catalysts at room temperature. Cysteine-containing

  2H-Azirine-2-caboxamides被设计为在非常温和的反应条件下充当新型的双功能硫醇连接基。2H-叠氮基的CN双键的裂解通过硫醇加成和开环过程原位提供氨基酰胺官能团。在室温下不存在任何催化剂的情况下，它可与各种硫醇和2H-叠氮基一起使用。还证明了含半胱氨酸的肽可以在完全水溶液中有效地起作用。
• An Azirine Strategy for the Synthesis of Alkyl 4-Amino-5-(trifluoromethyl)-1H-pyrrole-2-carboxylates
  作者：Alexander Khlebnikov、Liya Funt、Olesya Tomashenko、Mikhail Novikov

  DOI：10.1055/s-0037-1610840

  日期：2018.12

  alkyl 4-amino-3-aryl-1-methyl-5-(trifluoromethyl)-1H-pyrrole-2-carboxylates via methylation/hydrazinolysis. 1-(3,3,3-Trifluoro-2,2-dihydroxypropyl)pyridin-1-ium bromide serves as a trifluoromethyl-containing building block for the preparation of trifluoromethyl-substituted aminopyrroles based on the 2H-azirine ring expansion strategy. The primary products, 3-aryl-2-(methoxycarbonyl)-4-(pyridin-1-ium

  摘要 1-（3,3,3-三氟-2,2-二羟丙基）吡啶鎓-1-溴化物用作含三氟甲基的结构单元，用于基于2 H-叠氮基扩环策略制备三氟甲基取代的氨基吡咯。主要产物3-芳基-2-（甲氧基羰基）-4-（吡啶-1-基-1-基）-5-（三氟甲基）吡咯-1-化物可通过H 2 / PtO 2氢化形成3-芳基-4-（哌啶-1-基）-5-（三氟甲基）-1 H-吡咯-2-羧酸烷基酯并转化成4-氨基-3-芳基-1-甲基-5-（三氟甲基）烷基-1 H-吡咯-2-羧酸盐通过甲基化/肼解作用。 1-（3,3,3-三氟-2,2-二羟丙基）吡啶鎓-1-溴化物用作含三氟甲基的结构单元，用于基于2 H-叠氮基扩环策略制备三氟甲基取代的氨基吡咯。主要产物3-芳基-2-（甲氧基羰基）-4-（吡啶-1-基-1-基）-5-（三氟甲基）吡咯-1-化物可通过H 2 / PtO 2氢化形成3-芳基-4-（哌啶-1-基）-5-（三氟甲基）-1
• 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。