N-Boc-5-methyl-N-(prop-2-yn-1-yl)pyridin-2-amine | 1284210-52-1

• 分子结构分类: 有机化合物 - 有机杂环化合物 - 吡啶及其衍生物
• 英文名称: N-Boc-5-methyl-N-(prop-2-yn-1-yl)pyridin-2-amine
• 英文别名: tert-butyl N-(5-methylpyridin-2-yl)-N-prop-2-ynylcarbamate
• CAS: 1284210-52-1
• 化学式: C₁₄H₁₈N₂O₂
• 分子量: 246.309
• InChiKey: WJQJHGJNXYJPGL-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  2.4
• 重原子数：
  18
• 可旋转键数：
  4
• 环数：
  1.0
• sp3杂化的碳原子比例：
  0.43
• 拓扑面积：
  42.4
• 氢给体数：
  0
• 氢受体数：
  3

反应信息

• 作为反应物：
  描述：

  N-Boc-5-methyl-N-(prop-2-yn-1-yl)pyridin-2-amine 在 sodium acetate 、 三氟乙酸 、 potassium iodide 、 sodium hydroxide 、 palladium(II) iodide 作用下， 以 乙醚 、 二氯甲烷 为溶剂， 100.0 ℃ 、1.6 MPa 条件下， 反应 1.0h， 生成 methyl 2-(6-methylimidazo[1,2-a]pyridin-3-yl)acetate
  参考文献：
  名称：

  多组分碘化钯催化氧化烷氧羰基化法合成发光熔融咪唑双环乙酸酯

  摘要：

  介绍了一种重要的稠合咪唑双环乙酸酯的新的多组分催化方法，该方法的核心存在于许多生物活性成分中。它基于容易获得的N-杂环炔丙基胺衍生物的顺序环化-烷氧基羰基化-异构化反应，该反应是在氧化条件下，使用由PdI 2（1 mol％）和KI（1当量）组成的简单催化体系，在在20°C的4：1混合CO-空气中于100°C下存在AcONa作为添加剂（1当量）。在优化的条件下，数个N-（prop-2-yn-1-基）吡啶-2-胺被平稳地转化为烷基2-（咪唑[1,2- a]] pyridin-3-yl）acetate获得适当收率（51–77％）。该方法也适用于转化ñ - （丙-2-炔-1-基）嘧啶-2-胺成2-（咪唑并[1,2一]嘧啶-3-基）乙酸乙酯和ñ - （丙-2-炔-1-基）吡嗪-2-胺转化为2-（咪唑并[1,2 - a ]吡嗪-3-基）乙酸盐。一些新合成的双环衍生物显示出有希望的发光性质。

  DOI：

  10.1002/cctc.202001693
• 作为产物：
  描述：

  2-(BOC- 氨基)-5-甲基吡啶 、 3-溴丙炔 在 sodium hydride 作用下， 以 N,N-二甲基甲酰胺 、 甲苯 为溶剂， 反应 16.0h， 以72%的产率得到N-Boc-5-methyl-N-(prop-2-yn-1-yl)pyridin-2-amine
  参考文献：
  名称：

  A multicomponent palladium-catalyzed carbonylative approach to imidazopyridinyl-N,N-dialkylacetamides

  摘要：

  A novel, multicomponent approach to 2-(imidazo[1,2-a]pyridin-3-yl)-N,N-dialkylacetamides (very important class of fused heterocyclic derivatives, known to act on central nervous system by enhancing the activity of the GABA) is reported. It is based on the carbonylation reaction of N-Boc-(prop-2-yn-1yl)pyridin-2-amines carried out in the presence of secondary amines (2-3 equiv) under oxidative conditions, using oxygen (from air) as oxidant (4:1 CO-air, total pressure 20 atm) and PdI2/KI as the catalytic system (0.33-1 mol% of PdI2 and 0.5 equiv of KI) in MeCN as the solvent at 100 degrees C. The process leads to the target compounds in good to high yields (67-90%) through an ordered sequence of steps, occurring in situ under the reaction conditions: Boc-deprotection of the substrate is followed by PdI2/KI-catalyzed oxidative monoaminocarbonylation of the terminal triple bond (or vice versa) to give a 2-ynamide intermediate, which then undergoes intramolecular aza-Michael reaction and isomerization. (C) 2020 Elsevier Inc. All rights reserved.

  DOI：

  10.1016/j.jcat.2020.03.026

文献信息

• Water mediated deprotective intramolecular hydroamination of N-propargylaminopyridines: synthesis of imidazo[1,2-a]pyridines
  作者：Darapaneni Chandra Mohan、Niraj B. Sarang、Subbarayappa Adimurthy

  DOI：10.1016/j.tetlet.2013.08.112

  日期：2013.11

  Metal-free synthesis of substituted imidazole [1,2-alpha]dpyridines from deprotective N-(prop-2-yn-1-yl)pyridin-2-amines in water is elucidated. Electron releasing substituents on pyridine ring provided pure products in quantitative yields without separation by column chromatography. (C) 2013 Elsevier Ltd. All rights reserved.
• A Base Promoted Cyclization of <i>N</i>-Propargylaminopyridines. Synthesis of Imidazo[1,2-<i>a</i>]pyridine Derivatives
  作者：Suren Husinec、Rade Markovic、Milos Petkovic、Veselin Nasufovic、Vladimir Savic

  DOI：10.1021/ol200508x

  日期：2011.5.6

  A base promoted cyclization of the protected N-propargylaminopyridines was shown to be an efficient method for the preparation of imidazo[1,2-a] pyridine derivatives. The reactions were carried out with a small excess of base, at room temperature or slightly above producing the heterocyclic products in moderate to good yields. The stereoelectronic properties of substituents on the pyridine ring were shown to influence the cyclization process.
• Synthesis of Luminescent Fused Imidazole Bicyclic Acetic Esters by a Multicomponent Palladium Iodide‐Catalyzed Oxidative Alkoxycarbonylation Approach
  作者：Lucia Veltri、Tommaso Prestia、Patrizio Russo、Catia Clementi、Paola Vitale、Fausto Ortica、Bartolo Gabriele

  DOI：10.1002/cctc.202001693

  日期：2021.2.5

  derivatives, carried out under oxidative conditions using a simple catalytic system consisting of PdI2 (1 mol%) in conjunction with KI (1 equiv.), in the presence of AcONa as additive (1 equiv.) at 100 °C under 20 bar of a 4 : 1 mixture CO‐air. Under the optimized conditions, several N‐(prop‐2‐yn‐1‐yl)pyridin‐2‐amines were smoothly converted into alkyl 2‐(imidazo[1,2‐a]pyridin‐3‐yl)acetates in fair yields

  介绍了一种重要的稠合咪唑双环乙酸酯的新的多组分催化方法，该方法的核心存在于许多生物活性成分中。它基于容易获得的N-杂环炔丙基胺衍生物的顺序环化-烷氧基羰基化-异构化反应，该反应是在氧化条件下，使用由PdI 2（1 mol％）和KI（1当量）组成的简单催化体系，在在20°C的4：1混合CO-空气中于100°C下存在AcONa作为添加剂（1当量）。在优化的条件下，数个N-（prop-2-yn-1-基）吡啶-2-胺被平稳地转化为烷基2-（咪唑[1,2- a]] pyridin-3-yl）acetate获得适当收率（51–77％）。该方法也适用于转化ñ - （丙-2-炔-1-基）嘧啶-2-胺成2-（咪唑并[1,2一]嘧啶-3-基）乙酸乙酯和ñ - （丙-2-炔-1-基）吡嗪-2-胺转化为2-（咪唑并[1,2 - a ]吡嗪-3-基）乙酸盐。一些新合成的双环衍生物显示出有希望的发光性质。
• A multicomponent palladium-catalyzed carbonylative approach to imidazopyridinyl-N,N-dialkylacetamides
  作者：Lucia Veltri、Patrizio Russo、Tommaso Prestia、Paola Vitale、Roberto Romeo、Bartolo Gabriele

  DOI：10.1016/j.jcat.2020.03.026

  日期：2020.6

  A novel, multicomponent approach to 2-(imidazo[1,2-a]pyridin-3-yl)-N,N-dialkylacetamides (very important class of fused heterocyclic derivatives, known to act on central nervous system by enhancing the activity of the GABA) is reported. It is based on the carbonylation reaction of N-Boc-(prop-2-yn-1yl)pyridin-2-amines carried out in the presence of secondary amines (2-3 equiv) under oxidative conditions, using oxygen (from air) as oxidant (4:1 CO-air, total pressure 20 atm) and PdI2/KI as the catalytic system (0.33-1 mol% of PdI2 and 0.5 equiv of KI) in MeCN as the solvent at 100 degrees C. The process leads to the target compounds in good to high yields (67-90%) through an ordered sequence of steps, occurring in situ under the reaction conditions: Boc-deprotection of the substrate is followed by PdI2/KI-catalyzed oxidative monoaminocarbonylation of the terminal triple bond (or vice versa) to give a 2-ynamide intermediate, which then undergoes intramolecular aza-Michael reaction and isomerization. (C) 2020 Elsevier Inc. All rights reserved.