E-6-iodo-1-phenyl-1-hexene | 157723-90-5

• 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: E-6-iodo-1-phenyl-1-hexene
• 英文别名: [(E)-6-iodohex-1-enyl]benzene
• CAS: 157723-90-5
• 化学式: C₁₂H₁₅I
• 分子量: 286.156
• InChiKey: DQRVMDRQYBWMAX-XBXARRHUSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  5.2
• 重原子数：
  13
• 可旋转键数：
  5
• 环数：
  1.0
• sp3杂化的碳原子比例：
  0.33
• 拓扑面积：
  0
• 氢给体数：
  0
• 氢受体数：
  0

反应信息

• 作为反应物：
  描述：

  E-6-iodo-1-phenyl-1-hexene 在 N-氯代丁二酰亚胺 、 potassium carbonate 作用下， 以 二氯甲烷 、 N,N-二甲基甲酰胺 为溶剂， 24.0 ℃ 、101.33 kPa 条件下， 反应 8.0h， 生成 (E)-N-chloro-6-phenyl-N-(prop-2-yn-1-yl)hex-5-en-1-amine
  参考文献：
  名称：

  中性氨基自由基的无锡还原串联环化反应的合成与计算研究。

  摘要：

  在无锡​​还原环化条件下，构象无偏的炔丙基戊基自由基的5- exo，5- exo环化反应具有优异的收率，化学选择性和非对映选择性，而不受电子环境和各种烯烃取代基导致的中间自由基稳定性的影响。这些条件避免了缓慢加入引发剂和还原剂的需要。相比之下，类似的6-exo，5-exo环化需要具有中等自由基稳定性的取代基，以避免产物过早还原。这些实验结果通过计算得到了证实，该计算进一步建立了这些无氨基团在暴露于无锡环化条件下的反应性。

  DOI：

  10.1021/acs.orglett.8b02456
• 作为产物：
  描述：

  phenyl-6 hexene-5 ol-1 (E) 在 吡啶 、 sodium iodide 作用下， 以 二氯甲烷 、 丙酮 为溶剂， 反应 12.0h， 生成 E-6-iodo-1-phenyl-1-hexene
  参考文献：
  名称：

  Regiochemical and stereochemical studies on halocyclization reactions of unsaturated sulfides

  摘要：

  The regiochemistry and stereochemistry for the halocyclization reactions of unsaturated benzyl sulfides have been examined as a function of tether length, type of unsaturation (carbon-carbon double bond versus carbon-carbon triple bond), substituents, and halogenating agent. Alkenyl sulfides were found to react with iodine or bromine at room temperature to give five-membered ring cycloadducts exclusively over those having four-membered rings, while for larger systems, six-membered ring products are formed preferentially over their five-membered ring isomers and exclusively over the seven-membered ring adducts. The endo- versus exo-regioselectivity of these alkenyl sulfide ring closures most likely reflects the difference in thermodynamic stabilities of the beta-halo sulfide cycloadducts, which are able to equilibrate via a common episulfonium intermediate. The efficiency of the cyclization process markedly drops off for these alkenyl sulfides as the tether length increases beyond four intervening carbon centers. Thus, while the halogenations of 3-butenyl sulfides and 4-pentenyl sulfides give high yields of cycloadducts, those of 5-hexenyl sulfides afford only small amounts of cyclized products and large quantities of acyclic dibromides. Conversely the reactions of acetylenic sulfides with iodine give uniformly high yields and regiochemical control regardless of the tether length. Thus, 3-butynyl and 4-pentynyl sulfides cyclize cleanly to the five-membered ring while 5-hexynyl sulfides give exclusively the six-membered ring, The products arising from these alkynyl sulfide ring closures are believed to be formed under kinetic control. The methodology has been applied to the synthesis of unusual bicyclic beta-lactams related to the penicillin family of antibiotics.

  DOI：

  10.1021/jo00125a038

文献信息

• Anionic cyclization of olefinic alkyllithiums: ring closure of terminally substituted 5-hexenyllithiums.
  作者：William F. Bailey、Kaustubh V. Gavaskar

  DOI：10.1016/s0040-4020(01)90450-8

  日期：1994.1

  the corresponding iodides by lithium-iodine exchange with t-butyllithium at −78 °C. Although 6-alkyl-substituted 5-hexenyllithiums do not isomerize to five-membered rings upon warming, terminally substituted 5-hexenyllithiums bearing a moderately activating phenyl or trimethylsilyl group cleanly undergo a totally regiospecific 5-exo cyclization at sub-ambient temperatures to afford five membered rings

  在相应的碘化物中，通过在-78°C下与叔丁基锂进行锂碘交换，由相应的碘化物制备了一系列在苯基[C（6）]烯烃碳上具有苯基，三甲基甲硅烷基或环丙基取代基的5-己烯基锂。虽然6-烷基取代的5-己烯基锂在升温后不会异构化为五元环，但带有中等活化苯基或三甲基甲硅烷基的末端取代的5-己烯基锂在低于室温的温度下会干净地进行完全区域特异性的5 - exo环化反应，得到五个带有CHRLi部分的二元环可以被亲电子试剂俘获以提供高产率的官能化产物。6-环丙基-5-己烯基锂的环化伴随着三元环的开环。
• Bailey William F., Gavaskar Kaustubh V., Tetrahedron, 50 (1994) N 20, S 5957-5970
  作者：Bailey William F., Gavaskar Kaustubh V.

  DOI：——

  日期：——