(6-Bromo-1-chlorohexyl)benzene | 1010685-65-0

• 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: (6-Bromo-1-chlorohexyl)benzene
• CAS: 1010685-65-0
• 化学式: C₁₂H₁₆BrCl
• 分子量: 275.616
• InChiKey: SKMUAPISDYCXKL-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  4.5
• 重原子数：
  14
• 可旋转键数：
  6
• 环数：
  1.0
• sp3杂化的碳原子比例：
  0.5
• 拓扑面积：
  0
• 氢给体数：
  0
• 氢受体数：
  0

反应信息

• 作为产物：
  描述：

  三丁基苯基锡 、 6-溴-1-己烯 在 二(氰基苯)二氯化钯 、 copper dichloride 作用下， 以 乙醚 为溶剂， 反应 12.0h， 以54%的产率得到(6-Bromo-1-chlorohexyl)benzene
  参考文献：
  名称：

  Palladium-Catalyzed Oxidative Arylhalogenation of Alkenes: Synthetic Scope and Mechanistic Insights

  摘要：

  This article describes the development of a Pd-catalyzed reaction for the arylhalogenation (halogen = Cl or Br) of diverse alpha-olefins by oxidatively intercepting Mizoroki-Heck intermediates. These transformations afford synthetically useful 1,2- and 1,1-arylhalogenated products in good yields with good to excellent selectivities that can be modulated by changing the nature of the halogenating reagent and/or the reaction conditions. The selectivity of these reactions can be rationally tuned by (i) controlling the relative rates of oxidative functionalization versus beta-hydride elimination from equilibrating Pd-II-alkyl species and (ii) stabilization of organometallic Pd-II intermediates through the formation of pi-benzyl adducts. These arylhalogenations exhibit modest to excellent levels of stereoselectivity, and the key carbon-halogen bond-forming step proceeds with predominant retention of stereochemistry at carbon.

  DOI：

  10.1021/ja101851v

文献信息

• Oxidatively Intercepting Heck Intermediates:  Pd-Catalyzed 1,2- and 1,1-Arylhalogenation of Alkenes
  作者：Dipannita Kalyani、Melanie S. Sanford

  DOI：10.1021/ja0782798

  日期：2008.2.1

  communication describes the development of two Pd-catalyzed reactions for the arylchlorination of diverse α-olefins by oxidatively intercepting Heck intermediates. Depending on the nature of the oxidant and the reaction conditions, these transformations can afford synthetically useful 1,1- or 1,2-arylchlorinated products in good yields and with good to excellent selectivities. Preliminary mechanistic

  该通讯描述了两种 Pd 催化反应的发展，用于通过氧化拦截 Heck 中间体对不同的 α-烯烃进行芳基氯化。根据氧化剂的性质和反应条件，这些转化可以以良好的产率和良好的选择性提供合成有用的 1,1- 或 1,2- 芳基氯化产物。初步的机理研究表明，这些反应的选择性可以合理地调整 (i) 通过控制氧化官能化与 β-氢化物从平衡 PdII-烷基物种中消除的相对速率和 (ii) 通过 Pd 中间体的 π-苄基稳定化。
• Palladium-Catalyzed Oxidative Arylhalogenation of Alkenes: Synthetic Scope and Mechanistic Insights
  作者：Dipannita Kalyani、Andrew D. Satterfield、Melanie S. Sanford

  DOI：10.1021/ja101851v

  日期：2010.6.23

  This article describes the development of a Pd-catalyzed reaction for the arylhalogenation (halogen = Cl or Br) of diverse alpha-olefins by oxidatively intercepting Mizoroki-Heck intermediates. These transformations afford synthetically useful 1,2- and 1,1-arylhalogenated products in good yields with good to excellent selectivities that can be modulated by changing the nature of the halogenating reagent and/or the reaction conditions. The selectivity of these reactions can be rationally tuned by (i) controlling the relative rates of oxidative functionalization versus beta-hydride elimination from equilibrating Pd-II-alkyl species and (ii) stabilization of organometallic Pd-II intermediates through the formation of pi-benzyl adducts. These arylhalogenations exhibit modest to excellent levels of stereoselectivity, and the key carbon-halogen bond-forming step proceeds with predominant retention of stereochemistry at carbon.