12-chloro-2,2-dimethyldodecanitrile | 866926-60-5

• 分子结构分类: 有机化合物 - 有机氮化合物
• 英文名称: 12-chloro-2,2-dimethyldodecanitrile
• 英文别名: 12-chloro-2,2-dimethyldodecanenitrile
• CAS: 866926-60-5
• 化学式: C₁₄H₂₆ClN
• 分子量: 243.82
• InChiKey: QJEVIDWDOHUUER-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  5.8
• 重原子数：
  16
• 可旋转键数：
  10
• 环数：
  0.0
• sp3杂化的碳原子比例：
  0.93
• 拓扑面积：
  23.8
• 氢给体数：
  0
• 氢受体数：
  1

反应信息

• 作为产物：
  描述：

  1-溴-6-氯己烷 、 5-氰基-5-甲基己基溴化锌 在 tris(dibenzylideneacetone)dipalladium (0) 1,3-双(2,6-二异丙基苯基)氯化咪唑鎓 作用下， 以 四氢呋喃 、 N-甲基吡咯烷酮 为溶剂， 反应 24.0h， 以81%的产率得到12-chloro-2,2-dimethyldodecanitrile
  参考文献：
  名称：

  结合实验和计算方法对钯-N-杂环卡宾催化剂的合理设计

  摘要：

  描述了开发Pd-NHC催化剂的组合实验和计算方法。制备了一系列结合了富电子取代基和贫电子取代基的苯并咪唑基铱配体，并在Suzuki反应中进行了评估。最富电子的配体表现出最高的催化活性。基于此信息，开发了第一个烷基-烷基Negishi交叉偶联反应方案。对N，N′-二芳基-（4，5-二氢）咪唑基亚胺基鎓配体的评估显示出对金属中心周围的空间形貌的强烈依赖性。Negishi反应中活性最高的配体，其Pd（0）和PdCl 2的计算研究-复合物和相关结构是在B3LYP / DZVP和HF / 3-21G的理论水平上建模的。势能超表面随着配体尺寸的增加而变平。计算出卡宾/ Pd（0）加合物的结合能（约31–40 kcal mol -1），约为PH 3的结合能（约16 kcal mol -1）。使用AIM分析发现分子内相互作用较弱。

  DOI：

  10.1016/j.tet.2005.07.101

文献信息

• Room-Temperature Negishi Cross-Coupling of Unactivated Alkyl Bromides with Alkyl Organozinc Reagents Utilizing a Pd/<i>N</i>-Heterocyclic Carbene Catalyst
  作者：Niloufar Hadei、Eric Assen B. Kantchev、Christopher J. O'Brien、Michael G. Organ

  DOI：10.1021/jo051304c

  日期：2005.10.1

  A high-yielding cross-coupling reaction of unactivated alkyl bromides possessing beta-hydrogens with alkylzinc halides utilizing a Pd/N-heterocyclic carbene (NHC) catalyst at room temperature is described. A variety of Pd sources, Pd-2(dba)(3), Pd(OAc)(2), or PdBr2, with the commercially available ligand precursor 1,3-bis(2,6-diisopropylphenyl)imidazolium chloride (IPr center dot HCl) successfully coupled 1-bromo-3-phenylpropane with n-butylzinc bromide in THF/NMP. An investigation of different NHC precursors showed that the bulky 2,6-diisopropylphenyl moiety was necessary to achieve high coupling yields (75-85%). The corresponding ethyl analogue was moderately active (11%). A range of unsymmetrical NHC precursors were prepared and evaluated. The ligand precursor containing one 2,6-diisopropylphenyl and one 2,6-diethylphenyl afforded the coupling product in 47% yield, clearly suggesting a direct relationship between the steric topography created by the flanking N-substituents and catalyst activity. Under optimal conditions, a number of alkyl bromides and alkylzinc halides possessing common functional groups (amide, nitrile, ester, acetal, and alkyne) were effectively coupled (61-92%). It is noteworthy that beta-substituted alkyl bromides and alkylzinc halides successfully underwent cross-coupling. Also, under these conditions alkyl chlorides were unaffected.