N-(benzenesulfonyl)-N-(2-fluoro-1-phenylethyl)benzenesulfonamide | 1215017-01-8

• 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-(benzenesulfonyl)-N-(2-fluoro-1-phenylethyl)benzenesulfonamide
• CAS: 1215017-01-8
• 化学式: C₂₀H₁₈FNO₄S₂
• 分子量: 419.498
• InChiKey: KOSWDWQNUABTJQ-UHFFFAOYSA-N

物化性质

• 沸点：
  581.2±60.0 °C(Predicted)
• 密度：
  1.361±0.06 g/cm3(Predicted)

计算性质

• 辛醇/水分配系数(LogP)：
  4.1
• 重原子数：
  28
• 可旋转键数：
  7
• 环数：
  3.0
• sp3杂化的碳原子比例：
  0.1
• 拓扑面积：
  88.3
• 氢给体数：
  0
• 氢受体数：
  6

反应信息

• 作为产物：
  描述：

  苯乙烯 、 N-氟代双苯磺酰胺 在 palladium diacetate 、 6-benzhydryl-6'-methyl-2,2'-bipyridine 作用下， 以 1,4-二氧六环 为溶剂， 反应 15.0h， 以75%的产率得到N-(benzenesulfonyl)-N-(2-fluoro-1-phenylethyl)benzenesulfonamide
  参考文献：
  名称：

  高效合成大体积的2,2'-联吡啶和（S）-吡啶-恶唑啉配体

  摘要：

  与市售的配体相比，大体积的N，N '双齿配体可以提供具有增强的催化活性的催化剂。然而，直接合成有效范围广泛的这些配体的简单方法并不常见。在这项工作中，开发了一种简单有效的方法来合成庞大的N，N'-双齿配体，包括2,2'-联吡啶和对映体富集的吡啶-恶唑啉。Pd / NIXANTPHOS催化剂体系能够合成一系列庞大的2,2'-联吡啶基配体和（S）-吡啶恶唑啉基对映体富集的配体，收率良好或极好。配体已经在苯乙烯的氨基氟化中作了基准。

  DOI：

  10.1002/adsc.202001218

文献信息

• Regioselective Radical Aminofluorination of Styrenes
  作者：Hongwei Zhang、Yongcheng Song、Jinbo Zhao、Jingping Zhang、Qian Zhang

  DOI：10.1002/anie.201406797

  日期：2014.10.6

  The copper‐catalyzed radical aminofluorination of styrenes with N‐fluorobenzenesulfonimide (NFSI) is realized with high regioselectivity, thus affording aminofluorination products with regioselectivities opposite that of the palladium‐catalyzed and noncatalyzed processes. Preliminary mechanistic studies suggested the reaction went through a radical pathway and was supported by DFT calculations. In

  使用N-氟苯磺酰亚胺（NFSI）可以实现苯乙烯的铜催化自由基氨基氟化反应，具有很高的区域选择性，因此提供的氨基氟化产物的区域选择性与钯催化和非催化方法相反。初步的机理研究表明，该反应通过了自由基途径，并得到了DFT计算的支持。在这些反应中，NFSI既用作自由基氮源又用作自由基氟源，因此使其成为有吸引力的试剂。
• Palladium-catalyzed intermolecular fluoroesterification of styrenes: exploration and mechanistic insight
  作者：Haihui Peng、Zheliang Yuan、Hao-yang Wang、Yin-long Guo、Guosheng Liu

  DOI：10.1039/c3sc50690h

  日期：——

  A novel palladium-catalyzed intermolecular oxidative fluoroesterification of vinylarenes has been developed using NFSI, one of the mildest electrophilic fluorinating reagents. The reaction presents an efficient synthetic pathway to afford a series of α-monofluoromethylbenzyl carboxylates in good to excellent yields. Rather than following an electrophilic fluorination pathway, the reaction is initiated through oxidation of Pd(0) to a Pd(II) fluoride complex by NFSI, followed by fluoropalladation of a styrene to generate an α-monofluoromethylbenzyl–Pd intermediate. Generally, reductive elimination of benzyl–PdII complexes is favored with relatively strong oxy-nucleophiles to afford C–O bonds. This reaction, however, exhibited the opposite reactivity: strong acids with weak nucleophilicity, such as CF3CO2H and CCl3CO2H, were prone to afford the fluoroesterification product, while weak acids with strong nucleophilicity, such as HOAc and BzOH, did not deliver the C–O bond product. Further mechanistic studies determined that Csp3–Pd(O2CR), a key intermediate, was generated through ionic ligand exchange between benzyl–Pd(NZ2) and CF3CO2H, and the final C–O bond was possibly formed through reductive elimination of a high-valent Csp3–Pd(O2CR) complex via an SN2-type nucleophilic attack pathway.

  一种新型钯催化的乙烯基芳烃分子间氧化性氟酯化反应已被开发，使用的试剂是NFSI，即一种最温和的亲电氟化试剂。该反应提供了一条高效的合成途径，能够以良好至优异的产率获得一系列α-单氟甲基苄基羧酸酯。反应并非遵循亲电氟化途径，而是通过NFSI将Pd(0)氧化为Pd(II)氟化物配合物，随后进行氟钯化作用于苯乙烯生成α-单氟甲基苄基-Pd中间体。通常情况下，与相对较强的氧亲核试剂反应有利于实现苄基-PdII配合物的还原消除，从而形成C-O键。然而，在此反应中表现出了相反的反应性：易与强酸（弱亲核性）如CF3CO2H和CCI3CO2H形成氟酯化产物，而与强亲核性弱酸如HOAc和BzOH则无法形成C-O键产物。进一步的机理研究表明，关键中间体Csp3-Pd(O2CR)是通过苄基-Pd(NZ2)与CF3CO2H之间的离子配体交换生成的，最终的C-O键很可能是通过高氧化态Csp3-Pd(O2CR)配合物的还原消除形成的，该过程可能涉及SN2型亲核攻击路径。
• Qiu, Shuifa; Xu, Tao; Zhou, Juan, Journal of the American Chemical Society, 2010, vol. 132, p. 2856 - 2857
  作者：Qiu, Shuifa、Xu, Tao、Zhou, Juan、Guo, Yinlong、Liu, Guosheng

  DOI：——

  日期：——
• Highly Selective Pd-Catalyzed Intermolecular Fluorosulfonylation of Styrenes
  作者：Zheliang Yuan、Hao-Yang Wang、Xin Mu、Pinhong Chen、Yin-Long Guo、Guosheng Liu

  DOI：10.1021/ja5131676

  日期：2015.2.25

  A novel Pd-catalyzed intermolecular regio- and diastereoselective fluorosulfonylation of styrenes has been developed under mild conditions. This reaction exhibits a wide range of functional-group tolerance in styrenes and arylsulfinic acids to afford various beta-fluoro sulfones. Preliminary mechanistic study reveals an unusual mechanism, in which a high-valent (L2PdF)-F-III species side-selectively reacts with a benzylic carbon radical to deliver a C-F bond. This pathway is distinct from a previously reported radical fluorination reaction.
• Efficient Synthesis of Bulky 2,2’‐Bipyridine and ( <i>S</i> )‐Pyridine‐Oxazoline Ligands
  作者：Zhipeng Zheng、Patrick J. Walsh

  DOI：10.1002/adsc.202001218

  日期：2021.2.2

  N’‐bidentate ligands can furnish catalysts with enhanced catalytic activity compared to commercially available ligands. Straightforward methods to effectively synthesize a broad range of these ligands, however, are uncommon. In this work, a simple and efficient method is developed for the synthesis of bulky N,N’‐bidentate ligands, including 2,2’‐bipyridines and enantioenriched pyridine‐oxazolines. The

  与市售的配体相比，大体积的N，N '双齿配体可以提供具有增强的催化活性的催化剂。然而，直接合成有效范围广泛的这些配体的简单方法并不常见。在这项工作中，开发了一种简单有效的方法来合成庞大的N，N'-双齿配体，包括2,2'-联吡啶和对映体富集的吡啶-恶唑啉。Pd / NIXANTPHOS催化剂体系能够合成一系列庞大的2,2'-联吡啶基配体和（S）-吡啶恶唑啉基对映体富集的配体，收率良好或极好。配体已经在苯乙烯的氨基氟化中作了基准。