2-norbornylmagnesium chloride | 52152-53-1

• 分子结构分类: 有机化合物 - 脂质和类脂质分子 - 异戊烯醇脂质
• 英文名称: 2-norbornylmagnesium chloride
• CAS: 52152-53-1
• 化学式: C₇H₁₁ClMg
• 分子量: 154.922
• InChiKey: JNRTUGMJEDDEIL-UHFFFAOYSA-M

计算性质

• 辛醇/水分配系数(LogP)：
  2.45
• 重原子数：
  9.0
• 可旋转键数：
  1.0
• 环数：
  2.0
• sp3杂化的碳原子比例：
  1.0
• 拓扑面积：
  0.0
• 氢给体数：
  0.0
• 氢受体数：
  0.0

反应信息

• 作为反应物：
  描述：

  2-norbornylmagnesium chloride 、 mercury dichloride 以 乙醚 为溶剂， 生成 3-bicyclo[2.2.1]heptanyl(chloro)mercury
  参考文献：
  名称：

  Dimitrov, V.; Thiele, K.-H.; Radeglia, R., Zeitschrift fur Anorganische und Allgemeine Chemie

  摘要：

  DOI：

文献信息

• Kinetic resolution of racemic Grignard reagents by nickel-catalyzed asymmetric Grignard cross-coupling
  作者：Tamio Hayashi、Koichi Kanehira、Tsuyoshi Hioki、Makoto Kumada

  DOI：10.1016/0040-4039(81)80169-4

  日期：1981.1

  Racemic Grignard reagents, 2-phenylpropylmagnesium chloride and 2-norbornylmagnesium chloride were kinetically resolved by asymmetric cross-coupling with vinyl bromides in the presence of chiral phosphine-nickel catalysts to give optically active coupling products (~37% ee) and carboxylic acids after carbonation with carbon dioxide.

  外消旋格氏试剂，2-苯基丙基氯化镁和2-降冰片基氯化镁在手性膦-镍催化剂的存在下，通过与乙烯基溴的不对称交叉偶联而动力学拆分，从而在碳酸化后得到光学活性偶联产物（〜37％ee）和羧酸与二氧化碳。
• Non‐Planar Structures of Sterically Overcrowded Trialkylamines
  作者：Klaus Banert、Manuel Heck、Andreas Ihle、Tharallah Shoker、Michael Wörle、A. Daniel Boese

  DOI：10.1002/chem.202003933

  日期：2021.2.19

  trialkylamines without steric congestion, which is also signalized by the smaller heights of the NC3 pyramids (0.241–0.259 Å). There is no clear correlation between the heights of these pyramids and the degree of the steric crowding in the new amines, presumably because steric repulsion is partly compensated by dispersion interaction. In the cases of the two heterocyclic amines, the steric stress is smaller

  主要通过用格氏试剂处理N-氯代二烷基胺，合成了几种在氮原子上具有三个大烷基的胺，其空间拥挤度显着超过三异丙胺。六种情况，即叔丁基二异丙胺、1-金刚烷基叔丁基异丙胺、带有额外N-环己基或N-外-2-降冰片基取代基的二-1-金刚烷基胺，以及 2,2,6,6-四甲基哌啶具有N-环己基或N-新戊基的衍生物，生成了合适的单晶，使得X射线衍射研究和分子结构分析成为可能。四种非环胺采用三骨架构象，三个C−N−C角之和始终在351.1°至352.4°范围内。因此，这些胺被证明在结构上明显比三烷基胺更平坦，并且没有空间拥挤，这也可以通过 NC 3金字塔的较小高度（0.241-0.259 Å）来体现。这些金字塔的高度与新胺中的空间拥挤程度之间没有明显的相关性，大概是因为空间排斥部分地被分散相互作用补偿了。在两种杂环胺的情况下，空间应力较小，并且分子结构包括完全不同的构象。量子化学计算得出了空间拥挤的三烷基胺的精确气相结构，显示出
• Dimitrov, V.; Thiele, K.-H.; Schenke, D., Zeitschrift fur Anorganische und Allgemeine Chemie
  作者：Dimitrov, V.、Thiele, K.-H.、Schenke, D.

  DOI：——

  日期：——
• Reactions of Electron-Rich Arylpalladium Complexes with Olefins. Origin of the Chelate Effect in Vinylation Catalysis
  作者：M. Portnoy、Y. Ben-David、I. Rousso、D. Milstein

  DOI：10.1021/om00021a021

  日期：1994.9

  Reaction of (dippp)Pd(Ph)Cl(1) with norbornene or styrene yields (dippp)PdCl2 (8) and (dippp)Pd(eta(2)-olefin). Kinetic follow-up reveals fast formation of (dippp)Pd(phenylnorbornyl)Cl (10), followed by its slow decomposition, with k(insertion) = 0.50 x 10(-3) L mol(-1) s(-1) and k(decomposition) = 0.90 X 10(-4) S-1. Phenylnorbornane and (with styrene) stilbenes are also formed. Faster reaction is observed with (dppp)Pd(Ph)Br (2) and faster still with (dippe)Pd(Cl (4) to yield, in the latter case, the stable (dippe)Pd(phenylnorbornyl)Cl (18). The rates of these reactions are strongly solvent dependent (DMF >> dioxane), are strongly retarded by added Cl-, and are unaffected by added phosphine, indicating that halide dissociation, followed by olefin coordination and rate-determining olefin insertion, are involved. In contrast, reaction of trans-(P(i)Pr(2)(n)Bu)(2)Pd(Ph)X (X = Cl, 5; X = Br, 6) with norbornene (or styrene) involves phosphine dissociation and leads to formation of (P(i)Pr(2)(n)Bu)(2)Pd(H)X. In the case of norbornene, beta-carbon elimination of the unobserved intermediate phenylnorbornyl complexes followed by beta-H elimination yields 1-methylene-2-phenylcyclohexenes. Complexes of the ligand dippb are unique in that both eta(1) and eta(2) coordination modes are easily accessible. While reaction products are similar to those obtained with dippp and dippe complexes, dependence of the reaction rate on reaction variables is intermediate between those observed for complexes of chelating and monodentate phosphines. The implications of these findings on catalysis are outlined.