pyridin-2-yl(1a,2,7,7a-tetrahydro-1H-naphtho[2,3-b]azirin-1-yl)methanone | 1443674-17-6

• 分子结构分类: 有机化合物 - 有机杂环化合物
• 英文名称: pyridin-2-yl(1a,2,7,7a-tetrahydro-1H-naphtho[2,3-b]azirin-1-yl)methanone
• CAS: 1443674-17-6
• 化学式: C₁₆H₁₄N₂O
• 分子量: 250.3
• InChiKey: MEACWUCFTDWXKX-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  2.07
• 重原子数：
  19.0
• 可旋转键数：
  1.0
• 环数：
  4.0
• sp3杂化的碳原子比例：
  0.25
• 拓扑面积：
  32.97
• 氢给体数：
  0.0
• 氢受体数：
  2.0

反应信息

• 作为反应物：
  描述：

  pyridin-2-yl(1a,2,7,7a-tetrahydro-1H-naphtho[2,3-b]azirin-1-yl)methanone 在 tetrakis(dimethylamido)titanium(IV) 、 叔丁基过氧化氢 、 (R, R)-(salen)Co(II) 、 六氟异丙醇 、 苯甲酰氟 作用下， 以 甲基叔丁基醚 为溶剂， 反应 24.0h， 以56%的产率得到N-((2R,3R)-3-fluoro-1,2,3,4-tetrahydronaphthalen-2-yl)picolinamide
  参考文献：
  名称：

  Enantioselective fluoride ring opening of aziridines enabled by cooperative Lewis acid catalysis

  摘要：

  The enantioselective ring opening of aziridines using a latent source of HF is described. A combination of two Lewis acids, (salen)Co and an achiral Ti(IV) cocatalyst, provided optimal reactivity and enantioselectivity for the trans beta-fluoroamine product. The use of a chelating aziridine protecting group was crucial. Acyclic and cyclic meso N-picolinamide aziridines underwent fluoride ring opening in up to 84% ee, and the kinetic resolution of a piperidine-derived aziridine was performed with k(rel)=6.6. The picolinamide group may be readily removed without epimerization of the fluoroamine. Preliminary studies revealed a bimetallic mechanism wherein the chiral (salen)Co catalyst delivers the nucleophile and the Ti(IV) cocatalyst activates the aziridine. (C) 2013 Elsevier Ltd. All rights reserved.

  DOI：

  10.1016/j.tet.2013.01.062
• 作为产物：
  描述：

  2-吡啶甲酸 、 1a,2,7,7a-tetrahydro-1H-naphtho[2,3-b]azirine 在 4-二甲氨基吡啶 、 N,N'-二异丙基碳二亚胺 作用下， 以 二氯甲烷 为溶剂， 反应 16.0h， 生成 pyridin-2-yl(1a,2,7,7a-tetrahydro-1H-naphtho[2,3-b]azirin-1-yl)methanone
  参考文献：
  名称：

  Enantioselective fluoride ring opening of aziridines enabled by cooperative Lewis acid catalysis

  摘要：

  The enantioselective ring opening of aziridines using a latent source of HF is described. A combination of two Lewis acids, (salen)Co and an achiral Ti(IV) cocatalyst, provided optimal reactivity and enantioselectivity for the trans beta-fluoroamine product. The use of a chelating aziridine protecting group was crucial. Acyclic and cyclic meso N-picolinamide aziridines underwent fluoride ring opening in up to 84% ee, and the kinetic resolution of a piperidine-derived aziridine was performed with k(rel)=6.6. The picolinamide group may be readily removed without epimerization of the fluoroamine. Preliminary studies revealed a bimetallic mechanism wherein the chiral (salen)Co catalyst delivers the nucleophile and the Ti(IV) cocatalyst activates the aziridine. (C) 2013 Elsevier Ltd. All rights reserved.

  DOI：

  10.1016/j.tet.2013.01.062

文献信息

• Chiral magnesium(ii)-catalyzed asymmetric ring-opening of meso-aziridines with primary alcohols
  作者：Jun Li、Yuting Liao、Yulong Zhang、Xiaohua Liu、Lili Lin、Xiaoming Feng

  DOI：10.1039/c4cc02206h

  日期：——

  The asymmetric ring-opening of meso-aziridines with primary alcohols is realized using an N,N′-dioxide–Mg(OTf)2 complex as the catalyst. The desired vicinal trans-β-amino ethers are afforded in good yields and enantioselectivities. Aniline and water could also be used as the nucleophiles for the ring-opening in an identical catalyst system.

  以N,N′-二氧化物–Mg(OTf)2复合物作为催化剂，初级醇对meso-氮杂环丁烷的不对称开环反应得以实现。所需的邻位反式-β-氨基醚以良好的产率和不对称选择性获得。苯胺和水也可以作为在相同催化体系中的核亲电试剂用于开环反应。
• Catalytic Enantioselective Ring-Opening and Ring-Closing Reactions of 3-Isothiocyanato Oxindoles and <i>N</i>-(2-Picolinoyl)aziridines
  作者：Linqing Wang、Dongxu Yang、Dan Li、Rui Wang

  DOI：10.1021/acs.orglett.5b01291

  日期：2015.6.19

  applied to an asymmetric formal [3 + 3] cycloaddition reaction with aziridines for the first time. The reaction was efficiently mediated by an in situ generated magnesium catalyst employing (R)-3,3′-fluorous-BINOL as a simple chiral ligand. Serials of polycyclic frameworks could be obtained after a ring-closing step. The enantioenriched ring-opening product was also utilized to modified amino acids, peptides

  3-异硫氰酸根合吲哚已成功地首次用于与氮丙啶的不对称形式[3 + 3]环加成反应中。通过使用（R）-3，3'-氟-BINOL作为简单的手性配体的原位生成的镁催化剂有效地介导该反应。在闭环步骤之后可以获得多环框架的系列。富含对映体的开环产物也用于修饰氨基酸，肽和双功能有机催化剂。
• Mg^II -Catalyzed Desymmetrization Reaction of <i>meso</i> -Aziridines with Hydroxylamines: Synthesis of Novel Chiral 1,2-Diamine Skeletons
  作者：Dan Li、Dongxu Yang、Linqing Wang、Xihong Liu、Xianxing Jiang、Rui Wang

  DOI：10.1002/chem.201603898

  日期：2016.11.21

  for the first time. A series of novel chiral 1,2‐diamine skeletons were obtained in good yields and enantioselectivities. The reaction employed magnesium catalysis generated in situ from a simple oxazoline‐OH chiral ligand. Obviously, the diverse structures of the obtained chiral 1,2‐diamine compounds could allow them to be potential chiral ligands in future catalytic asymmetric synthesis studies.

  首次公开了Mg II催化的内消旋氮丙啶与羟胺的脱对称反应。以良好的收率和对映选择性获得了一系列新颖的手性1,2-二胺骨架。该反应采用由简单的恶唑啉-OH手性配体原位生成的镁催化。显然，获得的手性1,2-二胺化合物的不同结构可能使它们成为未来催化不对称合成研究中潜在的手性配体。
• Magnesium Catalysis Mediated Tetrazoles in Desymmetrization Reaction of Aziridines
  作者：Dan Li、Kezhou Wang、Linqing Wang、Yuan Wang、Pengxin Wang、Xin Liu、Dongxu Yang、Rui Wang

  DOI：10.1021/acs.orglett.7b01333

  日期：2017.6.16

  yields and good enantioselectivities. A new chiral ligand was synthesized from azetidine and (R)-BINOL and was employed in the current in situ generated magnesium catalyst. The Mg(II)-mediated desymmetrization reaction could be performed on gram scale under mild conditions and was transformed to chiral alkyl amines by a deprotection process.

  报道了镁催化的氮丙啶与取代的四唑的不对称开环反应。当前的协议进展顺利，并以高收率和良好的对映选择性提供了相应的去对称产物。由氮杂环丁烷和（R）-BINOL合成了一种新的手性配体，并用于当前的原位生成的镁催化剂中。Mg（II）介导的脱对称反应可以在温和的条件下以克为单位进行，并通过脱保护过程转化为手性烷基胺。
• Catalytic Asymmetric [8+3] Annulation Reactions of Tropones or Azaheptafulvenes with <i>meso</i> -Aziridines
  作者：Jianlin Zhang、Wanlong Xiao、Haipeng Hu、Lili Lin、Xiaohua Liu、Xiaoming Feng

  DOI：10.1002/chem.201803507

  日期：2018.9.12

  Highly enantioselective [8+3] high‐order cycloaddition reactions of tropones or azaheptafulvenes with meso‐aziridines were achieved by a desymmetrization/annulation process in the presence of chiral N,N′‐dioxide/Mg(OTf)2 complex. The corresponding tetrahydrocyclohepta[b][1,4]oxazines and tetrahydro‐1H‐cyclohepta‐ [b]‐pyrazines were obtained in good yields (66–98 %) with excellent diastereo‐ and enantioselectivities

  在手性N，N'-二氧化物/ Mg（OTf）2络合物存在下，通过去对称/环化过程实现了对偶氮酮或氮杂庚烯酮与内消旋氮杂环丁烷的高度对映选择性[8 + 3]高阶环加成反应。相应的四氢环庚[ b ] [1,4]恶嗪和四氢-1 H-环庚[[ b ]-吡嗪类化合物以良好的非对映和对映选择性（> 19：1 dr，90）获得了良好的收率（66-98％）。 –96％ee）。根据控制实验和催化剂的X射线晶体结构，提出了一种可能的过渡态模型，以阐明手性诱导的起源。