ethyl 4-(((perfluorobutyl)sulfonyl)oxy)benzoate | 32848-24-1

• 分子结构分类: 有机化合物 - 有机卤素化合物 - 卤代烷
• 英文名称: ethyl 4-(((perfluorobutyl)sulfonyl)oxy)benzoate
• 英文别名: 4-(Nonafluorobutylsulfonyloxy)benzoic acid ethyl ester；ethyl 4-(1,1,2,2,3,3,4,4,4-nonafluorobutylsulfonyloxy)benzoate
• CAS: 32848-24-1
• 化学式: C₁₃H₉F₉O₅S
• 分子量: 448.263
• InChiKey: NBKMVIZRRQEUBL-UHFFFAOYSA-N

物化性质

• 沸点：
  359.4±42.0 °C(Predicted)
• 密度：
  1.558±0.06 g/cm3(Predicted)

计算性质

• 辛醇/水分配系数(LogP)：
  4.9
• 重原子数：
  28
• 可旋转键数：
  8
• 环数：
  1.0
• sp3杂化的碳原子比例：
  0.46
• 拓扑面积：
  78
• 氢给体数：
  0
• 氢受体数：
  14

反应信息

• 作为反应物：
  描述：

  ethyl 4-(((perfluorobutyl)sulfonyl)oxy)benzoate 在 tris-(dibenzylideneacetone)dipalladium(0) 、 2-二叔丁基膦-2′,4′,6′-三异丙基-3,6-二甲氧基-1,1′-联苯 、 cesium fluoride 作用下， 以 甲苯 为溶剂， 反应 0.5h， 以119 mg的产率得到对氟苯甲酸乙酯
  参考文献：
  名称：

  One-Pot, Two-Step, Microwave-Assisted Palladium-Catalyzed Conversion of Aryl Alcohols to Aryl Fluorides via Aryl Nonaflates

  摘要：

  A convenient procedure for converting aryl alcohols to aryl fluorides via aryl nonafluorobutylsulfonates (ArONf) is presented. Moderate to good one-pot, two-step yields were achieved by this nonaflation and microwave-assisted, palladium-catalyzed fluorination sequence. The reductive elimination step was investigated by DFT calculations to compare fluorination with chlorination, proving a larger thermodynamic driving force for the aryl fluoride product. Finally, a key aryl fluoride intermediate for the synthesis of a potent HCV NS3 protease inhibitor was smoothly prepared with the novel protocol.

  DOI：

  10.1021/jo400255m
• 作为产物：
  描述：

  phenyl nonaflate 在 N-碘代丁二酰亚胺 、 硫酸 、 异丙基氯化镁 作用下， 以 四氢呋喃 为溶剂， 生成 ethyl 4-(((perfluorobutyl)sulfonyl)oxy)benzoate
  参考文献：
  名称：

  Aryl fluoroalkanesulfonate chemistry. A new approach to labelled arene elaboration

  摘要：

  DOI：

  10.1002/jlcr.1181

文献信息

• Barbier-Negishi Coupling of Secondary Alkyl Bromides with Aryl and Alkenyl Triflates and Nonaflates
  作者：Ke-Feng Zhang、Fadri Christoffel、Olivier Baudoin

  DOI：10.1002/anie.201711990

  日期：2018.2.12

  secondary alkyl bromides with aryl and alkenyl triflates and nonaflates has been developed. This challenging reaction was enabled by the use of a very bulky imidazole‐based phosphine ligand, which resulted in good yields as well as good chemo‐ and site selectivities for a broad range of substrates at room temperature and under non‐aqueous conditions. This reaction was extended to primary alkyl bromides

  已经开发出温和而实用的仲烷基溴化物与芳基和烯基三氟甲磺酸酯和壬二酸酯的Barbier-Negishi偶联。通过使用非常庞大的咪唑基膦配体，可以实现这一具有挑战性的反应，从而在室温下和非水条件下对多种底物产生了良好的收率以及良好的化学和位点选择性。通过使用类似的吡唑基配体，该反应扩展为伯烷基溴化物。
• Highly stereoselective and catalytic desulfitative C O and C I dienylation with sulfolenes: The importance of basic additives
  作者：Hang T. Dang、Viet D. Nguyen、Hoang H. Pham、Hadi D. Arman、Oleg V. Larionov

  DOI：10.1016/j.tet.2019.04.012

  日期：2019.6

  organic synthesis and materials science. We describe herein a palladium-catalyzed dienylation of aryl, heteroaryl, and vinyl triflates, nonaflates and iodides that were previously identified as recalcitrant substrates for the sulfolene-mediated catalytic dienylation. The method has now been successfully expanded to C-O and C-I dienylation, demonstrating broad scope with respect to sulfonates, iodides

  共轭二烯和多烯是天然产物的中心结构图案，也是有机合成和材料科学中的关键合成中间体。我们在本文中描述了芳基，杂芳基和乙烯基三氟甲磺酸酯，壬二酸酯和碘化物的钯催化的二烯基化，这些化合物先前已被确定为环丁二烯介导的催化二烯基化的顽固底物。该方法现已成功扩展到CO和CI二烯基化，在磺酸盐，碘化物和亚砜方面具有广阔的应用前景。反应进行时具有很高的区域选择性和立体选择性，并且效率受到碱性添加剂的强烈影响，因此系统地研究了其对反应性能的影响。
• Stereoselective Csp ³ −Csp ² Cross‐Couplings of Chiral Secondary Alkylzinc Reagents with Alkenyl and Aryl Halides
  作者：Juri Skotnitzki、Alexander Kremsmair、Daniel Keefer、Ye Gong、Regina Vivie‐Riedle、Paul Knochel

  DOI：10.1002/anie.201910397

  日期：2020.1.2

  We report palladium-catalyzed cross-coupling reactions of chiral secondary non-stabilized dialkylzinc reagents, prepared from readily available chiral secondary alkyl iodides, with alkenyl and aryl halides. This method provides α-chiral alkenes and arenes with very high retention of configuration (dr up to 98:2) and satisfactory overall yields (up to 76 % for 3 reaction steps). The configurational stability

  我们报告了手性仲非稳定的二烷基锌试剂的钯催化交叉偶联反应，该试剂由易于获得的手性仲烷基碘与烯基和芳基卤化物制备。该方法提供的α-手性烯烃和芳烃具有很高的构型保留率（dr高达98：2）和令人满意的总收率（3个反应步骤高达76％）。确定了这些手性不稳定的二烷基锌试剂的构型稳定性，并在25°C下超过了数小时。进行DFT计算以合理化催化循环中的立体保留。此外，在绝对立体化学的控制下，交叉偶联反应用于倍半萜（S）-和（R）-姜黄素的有效全合成中。
• Synthesis of multisubstituted pyrroles by ligand-controlled site-selective arylation and their transformation into multiarylated pyrrolines and pyrrolidines
  作者：Miyuki Yamaguchi、Sakiko Fujiwara、Yukiko Mori、Hideyuki Konishi、Kei Manabe

  DOI：10.1016/j.tet.2022.132962

  日期：2022.9

  Multisubstituted pyrroles were prepared by Pd-catalyzed site-selective arylation of 2,5-disubstituted 1H-pyrroles with aryl chlorides, triflates, or nonaflates. Site-selectivity of the reaction was controlled using appropriate ligands, and 2,2,5-trisubstituted 2H-pyrroles were synthesized via dearomative C2-arylation. Moreover, 2,3,5-trisubstituted 1H-pyrroles were successfully fabricated by direct

  多取代的吡咯是通过 Pd 催化的 2,5-二取代的 1 H-吡咯与芳基氯化物、三氟甲磺酸酯或九氟甲磺酸酯的位点选择性芳基化来制备的。使用适当的配体控制反应的位点选择性，并通过脱芳烃 C2-芳基化合成 2,2,5-三取代的 2 H-吡咯。此外，通过直接C3-芳基化成功制备了2,3,5-三取代的1 H-吡咯。这些芳基化可应用于带有芳基氯部分的药物。此外，2,2,5-三芳基-2 H-吡咯被转化为多芳基化吡咯啉和吡咯烷，可用于合成和药物化学。
• A General Method for Palladium-Catalyzed Reactions of Primary Sulfonamides with Aryl Nonaflates
  作者：Shashank Shekhar、Travis B. Dunn、Brian J. Kotecki、Donna K. Montavon、Steven C. Cullen

  DOI：10.1021/jo200443u

  日期：2011.6.3

  A general method for Pd-catalyzed sulfonamidation of aryl nonafluorobutanesulfonates (aryl nonaflates) is described. A biaryl phosphine ligand, t-BuXPhos, formed the most active catalyst, and K3PO4 in tert-amyl alcohol was found to be the optimal base solvent combination for the reaction. The reaction conditions were tolerant of various functional groups such as cyano, nitro, ester, aldehyde, ketone, chloride, carbamate, and phenol. Heterocyclic aryl nonaflates were found to be suitable coupling partners. High yields of the coupled products were obtained from the reactions between inherently disfavored substrates such as electron-rich nonaflates and electron-poor sulfonamides. Kinetic data suggest reductive elimination to be the rate-limiting step for the reaction. The only limitation of this methodology that we have identified is the inability of 2,6-disubstituted aryl nonaflates to efficiently participate in the reaction.