meso-3,4-Dichlor-hexan

• 分子结构分类: 有机化合物 - 有机卤素化合物 - 有机氯化物
• 英文名称: meso-3,4-Dichlor-hexan
• 英文别名: (3S,4R)-3,4-dichlorohexane
• 化学式: C₆H₁₂Cl₂
• 分子量: 155.067
• InChiKey: GBIMAWDSABONCC-OLQVQODUSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  3.3
• 重原子数：
  8
• 可旋转键数：
  3
• 环数：
  0.0
• sp3杂化的碳原子比例：
  1.0
• 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：

  meso-3,4-Dichlor-hexan 在 丙醇 、 氢氧化钾 、 氨 、 sodium 作用下， 生成 正-3-己烯
  参考文献：
  名称：

  The Quantitative Inversion of cis- and trans-Alkene Isomers: A New Synthesis of Normal cis-Alkenes¹

  摘要：

  DOI：

  10.1021/ja01151a099
• 作为产物：
  描述：

  反-3-已烯 在 1-己烯 、 (1,1'-ditetradecyl-3,3'-methylene-4-diimidazoline-2,2'-diylidene)trichloro(pyridine)palladium(IV) triflate 作用下， 生成 meso-3,4-Dichlor-hexan
  参考文献：
  名称：

  Pyridine-Assisted Chlorinations and Oxidations by Palladium(IV)

  摘要：

  The reactivity of the bis-NHC complex (LPdCl4)-Cl-IV (L = kappa(2)-[R-NHCCH2NHC-R] with R = C14H29) in chlorinations and oxidations of organic substrates was considerably increased in the presence of pyridine. For alkene chlorinations, this effect was due to the in situ formation of highly reactive (LPdCl3)-Cl-IV(py)(+), which was able to transfer Cl+ to the C=C bond in a ligand-mediated process (devoid of pi complexation), which did not require py dissociation. The enhanced reactivity in the presence of pyridine also extended to the oxidation of secondary and benzylic alcohols under mild conditions in a reaction where py served as a base, broadening the known scope of reactivity for Pd-IV complexes. (LPdCl3)-Cl-IV(py)(+) could be formed from Cl-/py exchange or from the oxidation of (LPdCl)-Cl-II(py)(+) by Cl-2. Taking advantage of the enhanced reactivities that pyridine coordination imparted on both Pd-II and Pd-IV complexes allowed for the catalytic chlorination of styrene with (LPdCl4)-Cl-IV as a sacrificial oxidant, thereby establishing the principal feasibility of Pd-II/Pd-IV catalyses that obviates Pd-II activations of the substrate.

  DOI：

  10.1021/om300007w

文献信息

• Bis-<i>N</i>-heterocyclic Carbene Palladium(IV) Tetrachloride Complexes: Synthesis, Reactivity, and Mechanisms of Direct Chlorinations and Oxidations of Organic Substrates
  作者：A. Scott McCall、Hongwang Wang、John M. Desper、Stefan Kraft

  DOI：10.1021/ja107342b

  日期：2011.2.16

  the preparation and isolation of novel octahedral CH(2)-bridged bis-(N-heterocyclic carbene)palladium(IV) tetrachlorides of the general formula LPd(IV)Cl(4) [L = (NHC)CH(2)(NHC)] from LPd(II)Cl(2) and Cl(2). In intermolecular, nonchelation-controlled transformations LPd(IV)Cl(4) reacted with alkenes and alkynes to 1,2-dichlorination adducts. Aromatic, benzylic, and aliphatic C-H bonds were converted into

  本文介绍了通式 LPd(IV)Cl(4) [L = (NHC)CH(2) )(NHC)] 来自 LPd(II)Cl(2) 和 Cl(2)。在分子间、非螯合控制的转化中，LPd(IV)Cl(4) 与烯烃和炔烃反应生成 1,2-二氯化加合物。芳香族、苄基和脂肪族 CH 键转化为 C-Cl 键。对 18VE Pd(IV) 配合物进行了烯烃二氯化的详细机理研究。正溶剂效应以及探索环己烯和氯化物浓度对烯烃氯化速率影响的动力学测量支持第一步中的 Pd(IV)-Cl 电离。来自各种烯烃的产品立体化学和产品分布也支持 Cl(+)-从五配位 Pd(IV)-中间体 LPd(IV)Cl(3)(+) 转移到烯烃。1-己烯/3-己烯竞争实验排除了沿反应坐标形成 π-配合物以及还原消除过程中原位生成的 Cl(2)。相反，很可能发生配体介导的从 LPd(IV)Cl(3)(+) 到 π 系统的直接 Cl(+)-转移。类似地，CH
• Chlorination of alkenes and alkynes with molybdenum(V) chloride
  作者：Joseph San Filippo、Allan F. Sowinski、Louis J. Romano

  DOI：10.1021/ja00839a067

  日期：1975.3
• Pyridine-Assisted Chlorinations and Oxidations by Palladium(IV)
  作者：A. Scott McCall、Stefan Kraft

  DOI：10.1021/om300007w

  日期：2012.5.14

  The reactivity of the bis-NHC complex (LPdCl4)-Cl-IV (L = kappa(2)-[R-NHCCH2NHC-R] with R = C14H29) in chlorinations and oxidations of organic substrates was considerably increased in the presence of pyridine. For alkene chlorinations, this effect was due to the in situ formation of highly reactive (LPdCl3)-Cl-IV(py)(+), which was able to transfer Cl+ to the C=C bond in a ligand-mediated process (devoid of pi complexation), which did not require py dissociation. The enhanced reactivity in the presence of pyridine also extended to the oxidation of secondary and benzylic alcohols under mild conditions in a reaction where py served as a base, broadening the known scope of reactivity for Pd-IV complexes. (LPdCl3)-Cl-IV(py)(+) could be formed from Cl-/py exchange or from the oxidation of (LPdCl)-Cl-II(py)(+) by Cl-2. Taking advantage of the enhanced reactivities that pyridine coordination imparted on both Pd-II and Pd-IV complexes allowed for the catalytic chlorination of styrene with (LPdCl4)-Cl-IV as a sacrificial oxidant, thereby establishing the principal feasibility of Pd-II/Pd-IV catalyses that obviates Pd-II activations of the substrate.
• The Quantitative Inversion of cis- and trans-Alkene Isomers: A New Synthesis of Normal cis-Alkenes¹
  作者：Melvern C. Hoff、Kenneth W. Greenlee、Cecil E. Boord

  DOI：10.1021/ja01151a099

  日期：1951.7