(6-Methyl-1-cyclohexen-1-yl)-nonafluorbutansulfonat | 84224-49-7

• 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: (6-Methyl-1-cyclohexen-1-yl)-nonafluorbutansulfonat
• 英文别名: 6-methylcyclohex-1-enyl nonaflate；(6-Methylcyclohexen-1-yl) 1,1,2,2,3,3,4,4,4-nonafluorobutane-1-sulfonate
• CAS: 84224-49-7
• 化学式: C₁₁H₁₁F₉O₃S
• 分子量: 394.258
• InChiKey: NHGYWUDLVRKTBM-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  5.1
• 重原子数：
  24
• 可旋转键数：
  5
• 环数：
  1.0
• sp3杂化的碳原子比例：
  0.82
• 拓扑面积：
  51.8
• 氢给体数：
  0
• 氢受体数：
  12

反应信息

• 作为反应物：
  描述：

  对甲苯磺酰胺 、 (6-Methyl-1-cyclohexen-1-yl)-nonafluorbutansulfonat 在 potassium phosphate 、 tris-(dibenzylideneacetone)dipalladium(0) 、 2-二-叔丁膦基-2',4',6'-三异丙基联苯 作用下， 以 2-甲基-2-丁醇 为溶剂， 生成 4-methyl-N-(6-methylcyclohexen-1-yl)benzenesulfonamide 、 4-methyl-N-(2-methylcyclohexen-1-yl)benzenesulfonamide
  参考文献：
  名称：

  A General Method for Palladium-Catalyzed Reactions of Primary Sulfonamides with Aryl Nonaflates

  摘要：

  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.

  DOI：

  10.1021/jo200443u
• 作为产物：
  描述：

  全氟丁基磺酰氟 、 2-甲基环己酮 在 1-(t-Bu-imino)-1,1,3,3,3-(Me2N)5-1λ⁵,3λ⁵-diphosphazene 作用下， 以 N,N-二甲基甲酰胺 为溶剂， 反应 65.0h， 以93%的产率得到(6-Methyl-1-cyclohexen-1-yl)-nonafluorbutansulfonat
  参考文献：
  名称：

  使用九氟丁烷-1-磺酰氟与磷腈碱组合从羰基化合物直接合成烯基九氟甲磺酸酯

  摘要：

  在内部淬灭剂九氟丁烷-1-磺酰氟的存在下，羰基化合物与磷腈碱的 α-去质子化提供相应的烯基九氟甲磺酸酯。新的通用方法从醛和环酮中提供了高产率的烯基壬二酸酯。然而，它不适用于非环酮，其九氟甲磺酸酯衍生物经过快速 E2 消除得到炔烃。由醛成功合成九氟甲磺酸酯需要仔细控制反应条件，以避免随后消除为炔烃。动力学控制能够实现高区域选择性，有利于衍生自环酮的最少取代的九氟甲磺酸酯区域异构体和衍生自醛的烯基九氟甲磺酸酯的适度 Z 选择性。

  DOI：

  10.1055/s-2007-991084

文献信息

• Hirsch, Elisabeth; Huenig, Siegfried; Reissig, Hans-Ulrich, Chemische Berichte, 1982, vol. 115, # 12, p. 3687 - 3696
  作者：Hirsch, Elisabeth、Huenig, Siegfried、Reissig, Hans-Ulrich

  DOI：——

  日期：——
• HIRSCH, E.;HUENIG, S.;REISSIG, H. -U., CHEM. BER., 1982, 115, N 12, 3687-3696
  作者：HIRSCH, E.、HUENIG, S.、REISSIG, H. -U.

  DOI：——

  日期：——
• 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.
• A Straightforward Synthesis of Alkenyl Nonaflates from Carbonyl Compounds Using Nonafluorobutane-1-sulfonyl Fluoride in Combination with Phosphazene Bases
  作者：Ilya Lyapkalo、Michael Vogel、Christian Stark

  DOI：10.1055/s-2007-991084

  日期：——

  nonafluorobutane-1-sulfonyl fluoride furnishes the corresponding alkenyl nonaflates. The new general method provides high yields of alkenyl nonaflates from aldehydes and cyclic ketones. However, it is not applicable to acyclic ketones whose nonaflate derivatives undergo fast E2 elimination to give alkynes. Successful synthesis of nonaflates from aldehydes requires carefully controlled reaction conditions to avoid

  在内部淬灭剂九氟丁烷-1-磺酰氟的存在下，羰基化合物与磷腈碱的 α-去质子化提供相应的烯基九氟甲磺酸酯。新的通用方法从醛和环酮中提供了高产率的烯基壬二酸酯。然而，它不适用于非环酮，其九氟甲磺酸酯衍生物经过快速 E2 消除得到炔烃。由醛成功合成九氟甲磺酸酯需要仔细控制反应条件，以避免随后消除为炔烃。动力学控制能够实现高区域选择性，有利于衍生自环酮的最少取代的九氟甲磺酸酯区域异构体和衍生自醛的烯基九氟甲磺酸酯的适度 Z 选择性。