N-allyl-4-formylbenzamide | 180422-59-7

• 分子结构分类: 有机化合物 - 苯类化合物 - 苯和取代衍生物
• 英文名称: N-allyl-4-formylbenzamide
• 英文别名: 4-Formyl-N-(prop-2-en-1-yl)benzamide；4-formyl-N-prop-2-enylbenzamide
• CAS: 180422-59-7
• 化学式: C₁₁H₁₁NO₂
• mdl: MFCD22683262
• 分子量: 189.214
• InChiKey: LCUSEGDEEHICCM-UHFFFAOYSA-N

物化性质

• 沸点：
  379.3±35.0 °C(Predicted)
• 密度：
  1.115±0.06 g/cm3(Predicted)

计算性质

• 辛醇/水分配系数(LogP)：
  1.3
• 重原子数：
  14
• 可旋转键数：
  4
• 环数：
  1.0
• sp3杂化的碳原子比例：
  0.09
• 拓扑面积：
  46.2
• 氢给体数：
  1
• 氢受体数：
  2

反应信息

• 作为反应物：
  描述：

  N-allyl-4-formylbenzamide 在 三甲基氯硅烷 、 碘苯二乙酸 作用下， 以 二氯甲烷 为溶剂， 反应 24.0h， 以75%的产率得到4-[5-(chloromethyl)-4,5-dihydrooxazol-2-yl]benzaldehyde
  参考文献：
  名称：

  Modular Preparation of 5-Halomethyl-2-oxazolines via PhI(OAc)₂-Promoted Intramolecular Halooxygenation of N-Allylcarboxamides

  摘要：

  A new method for the construction of oxazoline moiety was detailed. Using (diacetoxyiodo)benzene (PIDA) as the reaction promoter and halotrimethylsilane as the halogen source, intramolecular halooxygenation and halothionation of N-allylcarboxamides/N-allylcarbothioamides proceeded readily, leading : to the corresponding 5-halomethyloxazolines/5-halomethylthiazolines in good to excellent isolated yields. The 5-halomethyl products could be converted to different derivatives via conventional nucleophilic substitution methods. The reactions were carried out using easily available starting materials, and did not need harsh reaction conditions. All these features made this reaction a viable method for the construction of different oxazoline and thiazoline structures.

  DOI：

  10.1021/acs.joc.5b01832
• 作为产物：
  描述：

  N-烯丙基-4-溴苯甲酰胺 、 9-methyl-9H-fluorene-9-carbonyl chloride 在 dichloro(cycloocta-1,5-diene)palladium (II) 、 N-甲基二环己基胺 、 potassium formate 、 四丁基碘化铵 、 tricyclohexylphosphine tetrafluoroborate 、 bis(dibenzylideneacetone)-palladium⁽⁰⁾ 、 tri tert-butylphosphoniumtetrafluoroborate 作用下， 反应 18.0h， 以72%的产率得到N-allyl-4-formylbenzamide
  参考文献：
  名称：

  Reductive Carbonylation of Aryl Halides Employing a Two-Chamber Reactor: A Protocol for the Synthesis of Aryl Aldehydes Including ¹³C- and D-Isotope Labeling

  摘要：

  A protocol has been developed for conducting the palladium-catalyzed reductive carbonylation of aryl iodides and bromides using 9-methylfluorene-9-carbonyl chloride (COgen) as a source of externally delivered carbon monoxide in a sealed two-chamber system (COware), and potassium formate as the in situ hydride source. The method is tolerant to a wide number Of functional groups positioned on the aromatic ring, and it can be exploited for the isotope labeling of the aldehyde group. Hence, reductive carbonylations run with (13)COgen provide a facile access to C-13-labeled aromatic aldehydes, whereas with DCO2K, the aldehyde is specifically labeled with deuterium. Two examples of double isotopic labeling are also demonstrated. Finally, the method was applied to the specific carbon-13 labeling of the beta-amyloid binding compound, florbetaben.

  DOI：

  10.1021/jo400741t

文献信息

• Fluorocyclisation via I(I)/I(III) catalysis: a concise route to fluorinated oxazolines
  作者：Felix Scheidt、Christian Thiehoff、Gülay Yilmaz、Stephanie Meyer、Constantin G Daniliuc、Gerald Kehr、Ryan Gilmour

  DOI：10.3762/bjoc.14.88

  日期：——

  Herein, we describe a catalytic fluorooxygenation of readily accessible N-allylcarboxamides via an I(I)/I(III) manifold to generate 2-oxazolines containing a fluoromethyl group. Catalysis is conditional on the oxidation competence of Selectfluor®, whilst HF serves as both a fluoride source and Brønsted acid activator. The C(sp3)-F bond of the mono-fluoromethyl unit and the C(sp3)-O bond of the ring

  在本文中，我们描述了经由I（I）/ I（III）歧管容易产生的N-烯丙基羧酰胺的催化氟代氧化反应，以生成含有氟甲基的2-恶唑啉。催化条件取决于Selectfluor®的氧化能力，而HF既可作为氟化物源，又可作为布朗斯台德酸活化剂。单氟甲基单元的C（sp3）-F键与环的C（sp3）-O键成向斜关系排列，从而稳定了与附近的电子富集的σ键（σC- C→σ* CF和σC-H→σ* CO）。通过代表性实例的X射线晶体学分析确定了立体电子薄纱效应的这种表现。鉴于氟在药物研发中的重要性，其调节构象的能力以及2-恶唑啉骨架在自然界中的普遍性，
• Nickel-Catalyzed Regio- and Enantioselective Hydroamination of Unactivated Alkenes Using Carbonyl Directing Groups
  作者：Changseok Lee、Hyung-Joon Kang、Huiyeong Seo、Sungwoo Hong

  DOI：10.1021/jacs.2c02343

  日期：2022.5.25

  addition of an N–H bond to various alkenes via a direct catalytic method is a powerful way of synthesizing value-added chiral amines. Therefore, the enantio- and regioselective hydroamination of unactivated alkenes remains an appealing goal. Here, we report the highly enantio- and regioselective Ni-catalyzed hydroamination of readily available unactivated alkenes bearing weakly coordinating native

  通过直接催化方法将 N-H 键不对称加成到各种烯烃上是合成高附加值手性胺的有效方法。因此，未活化烯烃的对映选择性和区域选择性加氢胺化仍然是一个有吸引力的目标。在这里，我们报告了具有弱配位天然酰胺或酯的现成未活化烯烃的高度对映选择性和区域选择性 Ni 催化的加氢胺化。该方法对末端和内部未活化烯烃均适用，并且具有广泛的胺偶联伙伴范围。温和的反应过程非常适合复杂分子的后期功能化，并有可能获得对映体富集的 β- 或 γ- 氨基酸衍生物和 1,2- 或 1,3-二胺的模块化访问。
• Reductive Carbonylation of Aryl Halides Employing a Two-Chamber Reactor: A Protocol for the Synthesis of Aryl Aldehydes Including ¹³C- and D-Isotope Labeling
  作者：Signe Korsager、Rolf H. Taaning、Anders T. Lindhardt、Troels Skrydstrup

  DOI：10.1021/jo400741t

  日期：2013.6.21

  A protocol has been developed for conducting the palladium-catalyzed reductive carbonylation of aryl iodides and bromides using 9-methylfluorene-9-carbonyl chloride (COgen) as a source of externally delivered carbon monoxide in a sealed two-chamber system (COware), and potassium formate as the in situ hydride source. The method is tolerant to a wide number Of functional groups positioned on the aromatic ring, and it can be exploited for the isotope labeling of the aldehyde group. Hence, reductive carbonylations run with (13)COgen provide a facile access to C-13-labeled aromatic aldehydes, whereas with DCO2K, the aldehyde is specifically labeled with deuterium. Two examples of double isotopic labeling are also demonstrated. Finally, the method was applied to the specific carbon-13 labeling of the beta-amyloid binding compound, florbetaben.
• Modular Preparation of 5-Halomethyl-2-oxazolines via PhI(OAc)₂-Promoted Intramolecular Halooxygenation of <i>N</i>-Allylcarboxamides
  作者：Gong-Qing Liu、Chun-Hua Yang、Yue-Ming Li

  DOI：10.1021/acs.joc.5b01832

  日期：2015.11.20

  A new method for the construction of oxazoline moiety was detailed. Using (diacetoxyiodo)benzene (PIDA) as the reaction promoter and halotrimethylsilane as the halogen source, intramolecular halooxygenation and halothionation of N-allylcarboxamides/N-allylcarbothioamides proceeded readily, leading : to the corresponding 5-halomethyloxazolines/5-halomethylthiazolines in good to excellent isolated yields. The 5-halomethyl products could be converted to different derivatives via conventional nucleophilic substitution methods. The reactions were carried out using easily available starting materials, and did not need harsh reaction conditions. All these features made this reaction a viable method for the construction of different oxazoline and thiazoline structures.