cyclohexylidene(phenyl)methyl 4-methylbenzenesulfonate

• 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: cyclohexylidene(phenyl)methyl 4-methylbenzenesulfonate
• 英文别名: [Cyclohexylidene(phenyl)methyl] 4-methylbenzenesulfonate；[cyclohexylidene(phenyl)methyl] 4-methylbenzenesulfonate
• 化学式: C₂₀H₂₂O₃S
• 分子量: 342.459
• InChiKey: KMLVCLZNVGRIPM-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  5.4
• 重原子数：
  24
• 可旋转键数：
  4
• 环数：
  3.0
• sp3杂化的碳原子比例：
  0.3
• 拓扑面积：
  51.8
• 氢给体数：
  0
• 氢受体数：
  3

反应信息

• 作为反应物：
  描述：

  cyclohexylidene(phenyl)methyl 4-methylbenzenesulfonate 、 Isobutylmagnesium chloride 在 tris(dibenzylideneacetone)dipalladium(0) chloroform complex 、 (R)-(-)-1-[(S)-2-二苯基磷二茂铁乙基-二叔丁基磷 作用下， 以 乙醚 、 甲苯 为溶剂， 反应 16.0h， 以87%的产率得到(1-cyclohexylidene-3-methylbutyl)benzene
  参考文献：
  名称：

  Kumada Coupling of Aryl and Vinyl Tosylates under Mild Conditions

  摘要：

  Aryl and alkenyl tosylates are easily prepared, inexpensive and, thus, attractive for transition-metal-catalyzed couplings, but their reactivity is low. We report examples of mild, palladium-catalyzed coupling of aryl, alkenyl, and alkyl Grignard reagents with aryl and alkenyl tosylates. The resulting biaryls, vinylarenes, and alkylarenes were isolated in good to excellent yield. These couplings were conducted with a nearly equimolar ratio of the two reactants, and many examples were conducted at room temperature.

  DOI：

  10.1021/jo051394l
• 作为产物：
  描述：

  环己基苯基甲酮 、 4-甲苯磺酸酐 在 potassium tert-butylate 作用下， 以 四氢呋喃 为溶剂， 以28 %的产率得到cyclohexylidene(phenyl)methyl 4-methylbenzenesulfonate
  参考文献：
  名称：

  通过主基团催化构建酯当量的 α-乙烯基化反应用于构建四元中心

  摘要：

  公开了一种通过用硅烷基乙烯酮缩醛捕获乙烯基碳阳离子来构建空间充塞四级中心的方法。这种主要基团催化的 α-乙烯基化反应是有利的，因为获得这些充血基序的方法有限。此外，β，γ-不饱和羰基部分和四取代烯烃存在于各种生物活性天然产物和药物中，这种催化平台提供了一种使用简单且廉价的材料获取它们的方法。

  DOI：

  10.1021/acs.orglett.3c00535

文献信息

• 10.1021/acs.orglett.4c00837
  作者：Williams, Chloe G.、Nistanaki, Sepand K.、Dong, Krista、Lee, Woojin、Houk, Kendall N.、Nelson, Hosea M.

  DOI：10.1021/acs.orglett.4c00837

  日期：——

  interception of vinyl carbocations with allyl ethers. The reaction utilizes commercially available borate salts as catalysts and is effective at constructing sterically hindered C–C bonds. The reaction mechanism is studied experimentally and computationally to support a charge-accelerated [3,3] rearrangement of a silyloxonium cation. Our reaction is also applied to the highly stereoselective synthesis of fully

  我们报道了一种催化 C-O 偶联/Claisen 级联反应，该反应是通过用烯丙基醚拦截乙烯基碳阳离子来实现的。该反应利用市售的硼酸盐作为催化剂，可有效构建空间受阻的 C-C 键。通过实验和计算研究了反应机理，以支持水飞铵阳离子的电荷加速 [3,3] 重排。我们的反应也适用于完全取代的乙烯基醚的高度立体选择性合成。
• Kumada Coupling of Aryl and Vinyl Tosylates under Mild Conditions
  作者：Michael E. Limmert、Amy H. Roy、John F. Hartwig

  DOI：10.1021/jo051394l

  日期：2005.11.1

  Aryl and alkenyl tosylates are easily prepared, inexpensive and, thus, attractive for transition-metal-catalyzed couplings, but their reactivity is low. We report examples of mild, palladium-catalyzed coupling of aryl, alkenyl, and alkyl Grignard reagents with aryl and alkenyl tosylates. The resulting biaryls, vinylarenes, and alkylarenes were isolated in good to excellent yield. These couplings were conducted with a nearly equimolar ratio of the two reactants, and many examples were conducted at room temperature.
• α-Vinylation of Ester Equivalents via Main Group Catalysis for the Construction of Quaternary Centers
  作者：Chloe G. Williams、Sepand K. Nistanaki、Conner W. Wells、Hosea M. Nelson

  DOI：10.1021/acs.orglett.3c00535

  日期：2023.5.26

  A methodology for the construction of sterically congested quaternary centers via the trapping of vinyl carbocations with silyl ketene acetals is disclosed. This main group-catalyzed α-vinylation reaction is advantageous as methods to access these congested motifs are limited. Moreover, β,γ-unsaturated carbonyl moieties and tetrasubstituted alkenes are present in various bioactive natural products

  公开了一种通过用硅烷基乙烯酮缩醛捕获乙烯基碳阳离子来构建空间充塞四级中心的方法。这种主要基团催化的 α-乙烯基化反应是有利的，因为获得这些充血基序的方法有限。此外，β，γ-不饱和羰基部分和四取代烯烃存在于各种生物活性天然产物和药物中，这种催化平台提供了一种使用简单且廉价的材料获取它们的方法。