2-(1,1-dimethylethyl)-4-penten-1-yl p-toluenesulfonate | 132621-52-4

• 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: 2-(1,1-dimethylethyl)-4-penten-1-yl p-toluenesulfonate
• CAS: 132621-52-4
• 化学式: C₁₆H₂₄O₃S
• 分子量: 296.431
• InChiKey: IKFOTYARSZOWQA-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  3.94
• 重原子数：
  20.0
• 可旋转键数：
  6.0
• 环数：
  1.0
• sp3杂化的碳原子比例：
  0.5
• 拓扑面积：
  43.37
• 氢给体数：
  0.0
• 氢受体数：
  3.0

反应信息

• 作为反应物：
  描述：

  2-(1,1-dimethylethyl)-4-penten-1-yl p-toluenesulfonate 在 1,8-二氮杂双环[5.4.0]十一碳-7-烯 、 sodium iodide 作用下， 生成 2-tert-Butyl-1,4-pentadiene
  参考文献：
  名称：

  Highly selective trapping of unsymmetrical pentadienyl anions by silicon and tin electrophiles. Marked contrast between kinetic and thermodynamic control of product composition

  摘要：

  The nucleophilic reaction of lithium and potassium salts of five pentadienyl anions bearing sterically and/or coordinatively different groups at their unsymmetrical 2-position toward Me3SiCl and Me3SnBr is described. When the anion of the potassium salt was trapped by Me3SiCl, (Z)-4-substituted-pentadienylsilanes were obtained with high selectivity (87-100%). The lithium salt, however, gave a mixture of (E)- and (Z)-4-substituted-pentadienylsilanes. The coupling reaction proceeds under kinetic control, because the product composition from Si trapping reflected the structure of the parent dienyl anion and the steric interaction between the incoming Me3Si group and the substituent on the anion. In contrast, when the anion was trapped by Me3SnBr under the identical conditions, (Z)-2-substituted-pentadienyltins were formed with 60-96% selectivity. Only relatively small changes in product composition, as a function of the cation or the substituent on the anion, were observed. These results could be explained by thermodynamic controlling factors, including a 1,5-Me3Sn shift, and a redistribution of pentadienyl groups under basic conditions.

  DOI：

  10.1021/jo00006a011
• 作为产物：
  描述：

  Methyl 2-tert-butyl-4-pentenoate 在 吡啶 、 lithium aluminium tetrahydride 作用下， 以 四氢呋喃 、 氯仿 为溶剂， 生成 2-(1,1-dimethylethyl)-4-penten-1-yl p-toluenesulfonate
  参考文献：
  名称：

  Highly selective trapping of unsymmetrical pentadienyl anions by silicon and tin electrophiles. Marked contrast between kinetic and thermodynamic control of product composition

  摘要：

  The nucleophilic reaction of lithium and potassium salts of five pentadienyl anions bearing sterically and/or coordinatively different groups at their unsymmetrical 2-position toward Me3SiCl and Me3SnBr is described. When the anion of the potassium salt was trapped by Me3SiCl, (Z)-4-substituted-pentadienylsilanes were obtained with high selectivity (87-100%). The lithium salt, however, gave a mixture of (E)- and (Z)-4-substituted-pentadienylsilanes. The coupling reaction proceeds under kinetic control, because the product composition from Si trapping reflected the structure of the parent dienyl anion and the steric interaction between the incoming Me3Si group and the substituent on the anion. In contrast, when the anion was trapped by Me3SnBr under the identical conditions, (Z)-2-substituted-pentadienyltins were formed with 60-96% selectivity. Only relatively small changes in product composition, as a function of the cation or the substituent on the anion, were observed. These results could be explained by thermodynamic controlling factors, including a 1,5-Me3Sn shift, and a redistribution of pentadienyl groups under basic conditions.

  DOI：

  10.1021/jo00006a011

文献信息

• Microwave-assisted generation of alkoxyl radicals and their use in additions, β-fragmentations, and remote functionalizations
  作者：Jens Hartung、Kristina Daniel、Thomas Gottwald、Andreas Groß、Nina Schneiders

  DOI：10.1039/b603480b

  日期：——

  solvents affords alkoxyl radicals, which were identified by (i) spin adduct formation (EPR-spectroscopy) and (ii) fingerprint-type selectivities in intramolecular additions (stereoselective synthesis of disubstituted tetrahydrofurans), beta-fragmentations (formation of carbonyl compounds), and C,H-activation of aliphatic subunits, by delta-selective hydrogen atom transfer. C-Radicals formed from oxygen-centered

  N-（烷氧基）噻唑-2（3H）-硫酮在低吸收性溶剂中的微波辐射（2.45 GHz，300-500 W）提供烷氧基，其通过以下方法鉴定：（i）自旋加合物形成（EPR光谱）和（ii）通过δ-选择性氢原子转移在分子内加成（二取代的四氢呋喃的立体选择性合成），β-片段化（羰基化合物的形成）和脂族亚基的C，H-活化中的指纹类型选择性。由以氧为中心的中间体形成的C自由基被Bu（3）SnH，L-半胱氨酸乙酯，谷胱甘肽的还原形式（还原性俘获）捕获，或通过溴原子供体BrCCl（3）（杂原子功能化）进行研究结果表明，微波活化优于UV / Vis光解法和传导加热，可从N-（烷氧基）噻唑硫酮生成烷氧基自由基。到目前为止，它提供了最短的反应时间，并且可以显着减少捕集试剂的量。
• On the stereoselectivity of 4-penten-1-oxyl radical 5-exo-trig cyclizations
  作者：Jens Hartung、Kristina Daniel、Christian Rummey、Gerhard Bringmann

  DOI：10.1039/b611473c

  日期：——

  Ring closure reactions were investigated in a combined computational (density functional theory) and experimental study, to uncover the origin of diastereoselection in 5-exo-trig cyclizations of methyl and tert-butyl-substituted 4-penten-1-oxyl radicals. Selectivity data were calculated on the basis of transition state theory, the Curtin-Hammett principle, and Maxwell-Boltzmann statistics, to provide

  在组合的计算（密度泛函理论）和实验研究中对闭环反应进行了研究，以揭示甲基和叔丁基取代的4-戊烯-1-氧基自由基的5-exo-trig环化中的非对映选择性的起源。选择性数据是根据过渡态理论，Curtin-Hammett原理和Maxwell-Boltzmann统计数据计算得出的，以提供计算出的顺反比与实验性顺反比之间的出色相关性。数据表明，CH 3和C（CH 3）3基团产生的2,3-反式，2,4-顺式和2,5-反式-非对映异构体沿着取代基位置1 <2 <3增大，其效果叔丁基取代基的数目更明显。理论指出，有利的环化方式是通过中间体进行的，该中间体的特征是原子C2和C3从O1（自由基中心）/ C5（烯烃C）/ C4（烯丙基C）的平面向相反的方向偏移。这种安排允许烷基取代基和= CH2实体采用与最少和最不严重的向斜和间平面相互作用相关的位置。基于杂环的构象特征，提出了一种过渡结构符号，该中间体在结构