pent-4-enyl benzo[b]thiophene-3-carboxylate | 1160843-12-8

• 分子结构分类: 有机化合物 - 有机杂环化合物 - 苯并噻吩类
• 英文名称: pent-4-enyl benzo[b]thiophene-3-carboxylate
• 英文别名: Pent-4-enyl 1-benzothiophene-3-carboxylate
• CAS: 1160843-12-8
• 化学式: C₁₄H₁₄O₂S
• 分子量: 246.33
• InChiKey: MOSNRSIFWYBSHM-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  4.3
• 重原子数：
  17
• 可旋转键数：
  6
• 环数：
  2.0
• sp3杂化的碳原子比例：
  0.21
• 拓扑面积：
  54.5
• 氢给体数：
  0
• 氢受体数：
  3

反应信息

• 作为反应物：
  描述：

  pent-4-enyl benzo[b]thiophene-3-carboxylate 在 双(乙腈)氯化钯(II) 、 N-氯代丁二酰亚胺 、 三异丙基硅烷 、 水 、 C₁₄H₂₀N₂O₂ 、 三乙胺 作用下， 以 二氯甲烷 、 乙腈 为溶剂， 以88%的产率得到5-Chloropentyl 1-benzothiophene-3-carboxylate
  参考文献：
  名称：

  内烯烃催化远程卤化氢

  摘要：

  伯烷基卤化物在有机合成中作为精细化学品具有广泛的用途。烯烃的直接卤化是合成这些卤化物的最有效方法之一。内部烯烃，特别是来自炼油厂的异构体混合物，构成了容易获得且廉价的原料，并且是该合成最有吸引力的起始材料。然而，烯烃的卤化氢通常会产生支链烷基卤化物。没有直接从内部烯烃制备直链烷基卤化物的催化方法，更不用说从烯烃异构体的混合物中制备了。在这里，我们报告了在钯催化下烯烃的远程氧化卤化，末端和内部烯烃都可以有效地产生伯烷基卤化物。通过引入羟基来设计吡啶-恶唑啉配体对于实现出色的化学和区域选择性至关重要。该催化体系也适用于烷烃脱氢生成的烯烃异构体混合物，为研究廉价烷烃的高价值利用提供了窗口。

  DOI：

  10.1038/s41557-021-00869-x
• 作为产物：
  描述：

  1-苯并噻吩-3-羧酸 、 (4-propan-2-ylphenyl)methyl N,N'-di(propan-2-yl)carbamimidate 以 乙腈 为溶剂， 反应 0.08h， 以90%的产率得到pent-4-enyl benzo[b]thiophene-3-carboxylate
  参考文献：
  名称：

  Microwave-Assisted Ester Formation Using O-Alkylisoureas: A Convenient Method for the Synthesis of Esters with Inversion of Configuration

  摘要：

  The formation of carboxylic esters via reaction of carboxylic acids with O-alkylisoureas proceeds in excellent yields with very short reaction times when conducted in a monomode microwave synthesizer. Efficient processes were developed using preformed or commercially available isoureas derived from primary and secondary alcohols, with a reaction time of only 5 min or less. It was demonstrated that under these microwave conditions, ester formation proceeded in good yields with clean inversion of configuration where appropriate. The process was validated using menthol, a hindered substrate for S(N)2 reactions. In addition, starting from primary alcohols, ester formation was successfully accomplished using ail in situ isourea formation procedure. A polymer-assisted solution-phase procedure was also developed by employing preformed solid-supported isoureas and by an efficient "catch and release" ester formation procedure whereby primary alcohols were caught on resin as isoureas by reaction with immobilized carbodiimide and released as esters by subsequent treatment with a carboxylic acids.

  DOI：

  10.1021/jo900476y

文献信息

• Asymmetric Palladium‐Catalyzed Oxycarbonylation of Terminal Alkenes: Efficient Access to β‐Hydroxy Alkylcarboxylic Acids
  作者：Bing Tian、Xiang Li、Pinhong Chen、Guosheng Liu

  DOI：10.1002/anie.202104252

  日期：2021.6.25

  leading to high reactivity and excellent enantioselective control. Compared to the conventional methods, the reaction itself features alkenes as easily prepared starting materials, mild and operationally simple reaction conditions, and insensitivities to air and water. Moreover, this method allows for broad alkene substrate scope, excellent regio- and enantioselectivities, scalabilities and a wide array

  已经建立了一种新的 Pd II催化的烯烃对映选择性氧羰基化。Pyox 的 C-6 位带有乙基的配体在分子间氧化钯过程中起着重要作用，导致高反应性和出色的对映选择性控制。与传统方法相比，该反应本身的特点是烯烃作为原料容易制备，反应条件温和且操作简单，对空气和水不敏感。此外，该方法具有广泛的烯烃底物范围、优异的区域选择性和对映选择性、可扩展性和广泛的应用，并为方便和直接合成手性 β-羟基烷基羧酸/酯提供了有用的途径。
• Palladium-catalyzed intermolecular alkynylcarbonylation of unactivated alkenes: easy access to β-alkynylcarboxylic esters
  作者：Xiang Li、Pinhong Chen、Guosheng Liu

  DOI：10.1039/d1cc07092d

  日期：——

  A palladium-catalyzed intermolecular alkynylcarbonylation of unactivated alkenes has been established with ethynyl benziodoxolones (EBXs) as alkynylation reagents, providing β-alkynylcarboxylic esters efficiently from simple alkenes. The reaction features moderate to excellent regioselectivity and excellent functional group compatibility under mild reaction conditions.

  以乙炔基苯并氧戊环 (EBXs) 作为炔基化试剂，建立了钯催化的未活化烯烃的分子间炔基羰基化反应，从而有效地从简单烯烃中生成 β-炔基羧酸酯。该反应在温和的反应条件下具有中等至优异的区域选择性和优异的官能团相容性。
• Palladium(II)-Catalyzed Enantioselective Hydrooxygenation of Unactivated Terminal Alkenes
  作者：Xintuo Yang、Xiang Li、Pinhong Chen、Guosheng Liu

  DOI：10.1021/jacs.2c02753

  日期：2022.5.11

  A novel Pd(II)-catalyzed enantioselective Markovnikov hydrooxygenation of unactivated terminal alkenes using a substituted pyridinyl oxazoline (Pyox) ligand has been developed. Herein it was discovered that the (EtO)2MeSiH/BQ redox system is vital for the highly selective and efficient hydrooxygenation, where the alkylpalladium(II) species generated from enantioselective oxypalladation step is reduced

  已经开发了一种使用取代的吡啶基恶唑啉 (Pyox) 配体对未活化末端烯烃进行新型 Pd(II) 催化的对映选择性马尔科夫尼科夫加氢氧化反应。在此发现 (EtO) 2 MeSiH/BQ 氧化还原系统对于高选择性和高效的加氢氧化至关重要，其中对映选择性氧化钯化步骤产生的烷基钯 (II) 物质被硅烷还原。该方法提供了从易于获得的烯烃中高效获得光学纯醇酯的方法，具有优异的对映选择性，并具有广泛的底物范围。
• Palladium-Catalyzed Remote Hydro-Oxygenation of Internal Alkenes: An Efficient Access to Primary Alcohols
  作者：Xiang Li、Xintuo Yang、Pinhong Chen、Guosheng Liu

  DOI：10.1021/jacs.2c11428

  日期：2022.12.21
• Microwave-Assisted Ester Formation Using <i>O</i>-Alkylisoureas: A Convenient Method for the Synthesis of Esters with Inversion of Configuration
  作者：Alessandra Chighine、Stefano Crosignani、Marie-Claire Arnal、Mark Bradley、Bruno Linclau

  DOI：10.1021/jo900476y

  日期：2009.7.3

  The formation of carboxylic esters via reaction of carboxylic acids with O-alkylisoureas proceeds in excellent yields with very short reaction times when conducted in a monomode microwave synthesizer. Efficient processes were developed using preformed or commercially available isoureas derived from primary and secondary alcohols, with a reaction time of only 5 min or less. It was demonstrated that under these microwave conditions, ester formation proceeded in good yields with clean inversion of configuration where appropriate. The process was validated using menthol, a hindered substrate for S(N)2 reactions. In addition, starting from primary alcohols, ester formation was successfully accomplished using ail in situ isourea formation procedure. A polymer-assisted solution-phase procedure was also developed by employing preformed solid-supported isoureas and by an efficient "catch and release" ester formation procedure whereby primary alcohols were caught on resin as isoureas by reaction with immobilized carbodiimide and released as esters by subsequent treatment with a carboxylic acids.