1-(hexa-1,5-dien-2-yl)-4-methoxybenzene | 65912-66-5

• 分子结构分类: 有机化合物 - 苯类化合物 - 苯酚醚
• 英文名称: 1-(hexa-1,5-dien-2-yl)-4-methoxybenzene
• 英文别名: 1-Hexa-1,5-dien-2-yl-4-methoxybenzene；1-hexa-1,5-dien-2-yl-4-methoxybenzene
• CAS: 65912-66-5
• 化学式: C₁₃H₁₆O
• 分子量: 188.269
• InChiKey: BYFILICKSZTLQU-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  4.3
• 重原子数：
  14
• 可旋转键数：
  5
• 环数：
  1.0
• sp3杂化的碳原子比例：
  0.23
• 拓扑面积：
  9.2
• 氢给体数：
  0
• 氢受体数：
  1

反应信息

• 作为反应物：
  描述：

  1-(hexa-1,5-dien-2-yl)-4-methoxybenzene 、 1,1-二溴-2-2-二苯基环丙烷 在 四丁基硫酸氢铵 、 sodium hydroxide 作用下， 以 四氢呋喃 为溶剂， 反应 36.0h， 生成 1-(1-(but-3-enyl)-2-(2,2-diphenylvinylidene)cyclopropyl)-4-methoxybenzene
  参考文献：
  名称：

  Halogenation Reagents Initiating Ring Opening of Vinylidenecyclopropanes: Easy Access to Halogenated Tetrahydropyrans

  摘要：

  一种新的合成策略被开发出来，使用卤素化试剂（NBS、NIS和selectfluor）来启动与含有醇基链的二芳基乙烯基环丙烷（VDCPs）相关的环内开环反应。该方法在温和条件下提供了多种卤化四氢呱衍生物，产率中等至良好。基于先前的文献，提出了合理的反应机制，并仔细研究了底物范围。

  DOI：

  10.1055/s-0030-1259715
• 作为产物：
  描述：

  1-(4-methoxyphenyl)pent-4-en-1-ol 在 manganese(IV) oxide 、 potassium tert-butylate 作用下， 以 四氢呋喃 、 正己烷 为溶剂， 生成 1-(hexa-1,5-dien-2-yl)-4-methoxybenzene
  参考文献：
  名称：

  Incorporation of 2-Arylhexa-1,5-diene into Pentasil Zeolite:  A Distorted 1-Arylcyclohexane-1,4-diyl Radical Cation at Room Temperature

  摘要：

  Incorporation into a redox-active pentasil zeolite [(Na,H)-ZSM-5] converted 2-arylhexa-1,5-dienes (9a-c; aryl = phenyl, tolyl, anisyl) into 1-arylcyclohexane-1,4-diyl radical cations, 10a-c(.+). The ESR spectra of 10a-c(.+) (six lines, g = 2.0026; a = 9.0 G) indicated the presence of five essentially equivalent nuclei, indicating limited delocalization of spin and charge into the phenyl group. Sequestered in the pores of ZSM-5, the three species 10a-c(.+) are stable at room temperature, in striking contrast to the parent radical cation in cryogenic matrices: cyclohexane-1,4-diyl radical cation is converted to cyclohexene radical cation above 90 K. The structures of radical cation 10a(.+) (X = H) and of the unsubstituted parent were probed by density functional theory (DFT) and ab initio calculations.

  DOI：

  10.1021/jp046877s

文献信息

• Cyclization–endoperoxidation cascade reactions of dienes mediated by a pyrylium photoredox catalyst
  作者：Nathan J Gesmundo、David A Nicewicz

  DOI：10.3762/bjoc.10.128

  日期：——

  Triarylpyrylium salts were employed as single electron photooxidants to catalyze a cyclization–endoperoxidation cascade of dienes. The transformation is presumed to proceed via the intermediacy of diene cation radicals. The nature of the diene component was investigated in this context to determine the structural requirements necessary for successful reactivity. Several unique endoperoxide structures were synthesized in yields up to 79%.

  三芳基吡啶盐被用作单电子光氧化剂，催化二烯烃的环化-内过氧化级联反应。该转化被认为是通过二烯烃阳离子自由基的中间体进行的。在这一背景下，研究了二烯烃组分的性质，以确定成功反应所需的结构要求。合成了几种独特的内过氧化物结构，收率高达79%。
• Palladium-Catalyzed Hydrocarbonylative Cyclization of 1,5-Dienes
  作者：Suchen Zou、Bao Gao、Yao Huang、Tianze Zhang、Hanmin Huang

  DOI：10.1021/acs.orglett.9b02230

  日期：2019.8.16

  novel and atom-economic palladium-catalyzed isomerization-hydrocarbonylative cyclization reaction of 1,5-dienes to 2-alkylidenecyclopentanones has been developed, which provides a rapid and straightforward approach to 2-alkylidenecyclopentanones with high stereoselectivity. The reaction was found to proceed via alkene isomerization and selective hydrocarbonylative cyclization to generate 2-alkylidenecyclopentanones

  已经开发了一种新颖的，原子经济的钯催化的1,5-二烯到2-亚烷基环戊烷酮的异构化-羰基化环化反应，它为具有高立体选择性的2-亚烷基环戊烷酮提供了一种快速而直接的方法。发现该反应通过烯烃异构化和选择性的烃基化环化进行，以产生具有高选择性的2-亚烷基环戊酮。
• Reactions of Vinylidenecyclopropanes with Diphenyl Diselenide in the Presence of AIBN and Thermally-Induced Further Transformations
  作者：Wei Yuan、Yin Wei、Min Shi、Yuxue Li

  DOI：10.1002/chem.201103461

  日期：2012.1.27

  vinylidenecyclopropanes with diphenyl diselenide in the presence of AIBN and upon heating gives the corresponding bicyclo[3.1.0]hexane derivatives in good yields. These compounds undergo thermal‐induced radical 1,4‐hydrogen shifts through a ring‐opening pathway of allylic cyclopropane to give the corresponding cyclohexene derivatives stereoselectively in good yields at 200 °C (see scheme).

  自由基变换器：在AIBN存在下并加热后，将亚乙烯基环丙烷与二苯二硒化物化学转化，得到高收率的相应双环[3.1.0]己烷衍生物。这些化合物通过烯丙基环丙烷的开环途径经历热诱导的自由基1,4-氢转移，从而在200°C下以良好的产率立体选择性地生成相应的环己烯衍生物（参见方案）。
• Asymmetric Synthesis of Chiral Cyclopentanes Bearing an All-Carbon Quaternary Stereocenter by Zirconium-Catalyzed Double Carboalumination
  作者：Shiqing Xu、Chuan Wang、Masato Komiyama、Yasuhiko Tomonari、Ei-ichi Negishi

  DOI：10.1002/anie.201706198

  日期：2017.9.11

  All-carbon quaternary stereocenters: A zirconium-catalyzed double carboalumination of various unactivated 1,5-dienes provides efficient access to chiral cyclopentanes with two stereocenters, including one all-carbon quaternary stereocenter, through the formation of two new C−C bonds as well as one C−Al bond with high diastereo- and enantioselectivity.

  全碳四元立体中心：各种未活化的1,5-二烯经锆催化的双碳铝键合可通过形成两个新的C-C键，有效地利用两个立体中心（包括一个全碳四元立体中心）有效地接触手性环戊烷作为具有高非对映选择性和对映选择性的C-Al键。
• Kinetically Controlled Stereoselective Access to Branched 1,3-Dienes by Ru-Catalyzed Remote Conjugative Isomerization
  作者：Simone Scaringi、Clément Mazet

  DOI：10.1021/acscatal.1c02144

  日期：2021.7.2

  3-dienes is described. These kinetic products are obtained in high yields, good levels of regiocontrol, and high stereoselectivity. A broad range of functional groups and heterocycles are compatible with the mild reaction conditions, and isomerization is sustained over long distances. Control experiments support a metal-hydride mechanism consisting of iterative migratory insertions/β-H eliminations, which

  描述了提供支链 1,3-二烯的远程烯烃的 Ru 催化共轭异构化。这些动力学产物以高产率、良好的区域控制水平和高立体选择性获得。范围广泛的官能团和杂环与温和的反应条件相容，并且异构化持续长距离。对照实验支持由迭代迁移插入/β-H 消除组成的金属氢化物机制，该机制优先在末端烯烃位点启动。已经开发了两种使用 [Ru/Cu] 和 [Ru/Rh] 组合的一锅多金属选择性催化序列来说明该过程的合成潜力。