((R)-2-isopropyl-3-buten-1-yl)-n-nonanylamine

• 分子结构分类: 有机化合物 - 有机氮化合物
• 英文名称: ((R)-2-isopropyl-3-buten-1-yl)-n-nonanylamine
• 英文别名: N-[(2S)-2-propan-2-ylbut-3-enyl]nonan-1-amine
• 化学式: C₁₆H₃₃N
• 分子量: 239.445
• InChiKey: HZYXBRCJYQUFJQ-INIZCTEOSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  6
• 重原子数：
  17
• 可旋转键数：
  12
• 环数：
  0.0
• sp3杂化的碳原子比例：
  0.88
• 拓扑面积：
  12
• 氢给体数：
  1
• 氢受体数：
  1

反应信息

• 作为产物：
  描述：

  丙基氯化镁 、 1-Nonyl-2,5-dihydro-1H-pyrrole 在 (R)-ZrCl2 作用下， 以 四氢呋喃 为溶剂， 反应 12.0h， 以50%的产率得到((R)-2-isopropyl-3-buten-1-yl)-n-nonanylamine
  参考文献：
  名称：

  Enantio-, Diastereo-, and Regioselective Zirconium-Catalyzed Carbomagnesation of Cyclic Ethers with Higher Alkyls of Magnesium. Utility in Synthesis and Mechanistic Implications

  摘要：

  Zirconocene-catalyzed carbomagnesation reactions of cyclic ethers 4 and 7 with n-PrMgCl and n-BuMgCl afford homoallylic and bishomoallylic alcohols 5, 8, 9, and 11 in similar to 40% yield and exceptional levels of enantioselectivity and regiocontrol. Where n-BuMgCl is used as the alkylating agent, high levels of diastereochemical control are also observed (cf. 9 vs 10 in entries 4 and 5 of Table 1). Studies reported herein underline a number of important mechanistic issues: (i) Although zirconocene-alkene complexes 3 exist as a mixture of diastereomers in solution (syn and anti), it is only one of the isomers which reacts to afford the observed products. (ii) Whereas insertion of an alkene substrate into the unsymmetric complexes 3 and 18 proceeds with low levels of regioselectivity at 22 degrees C, at 70 degrees C high levels of regiocontrol are observed (cf. intermediacy of 20 vs 24 in Scheme 4). In this context, various mechanistic experiments shed light on factors that may be responsible for the observed temperature effect. (iii) Unusual modes of preference for the regioselectivity in beta-hydride abstraction of intermediate dialkylzirconocene are reported; these observations may be accounted for through consideration of the steric effects imposed by the cyclohexyl groups of the chiral ligand and the stereoelectronic requirements of the elimination reaction.

  DOI：

  10.1021/ja00132a009

文献信息

• Enantio-, Diastereo-, and Regioselective Zirconium-Catalyzed Carbomagnesation of Cyclic Ethers with Higher Alkyls of Magnesium. Utility in Synthesis and Mechanistic Implications
  作者：Mary T. Didiuk、Charles W. Johannes、James P. Morken、Amir H. Hoveyda

  DOI：10.1021/ja00132a009

  日期：1995.7

  Zirconocene-catalyzed carbomagnesation reactions of cyclic ethers 4 and 7 with n-PrMgCl and n-BuMgCl afford homoallylic and bishomoallylic alcohols 5, 8, 9, and 11 in similar to 40% yield and exceptional levels of enantioselectivity and regiocontrol. Where n-BuMgCl is used as the alkylating agent, high levels of diastereochemical control are also observed (cf. 9 vs 10 in entries 4 and 5 of Table 1). Studies reported herein underline a number of important mechanistic issues: (i) Although zirconocene-alkene complexes 3 exist as a mixture of diastereomers in solution (syn and anti), it is only one of the isomers which reacts to afford the observed products. (ii) Whereas insertion of an alkene substrate into the unsymmetric complexes 3 and 18 proceeds with low levels of regioselectivity at 22 degrees C, at 70 degrees C high levels of regiocontrol are observed (cf. intermediacy of 20 vs 24 in Scheme 4). In this context, various mechanistic experiments shed light on factors that may be responsible for the observed temperature effect. (iii) Unusual modes of preference for the regioselectivity in beta-hydride abstraction of intermediate dialkylzirconocene are reported; these observations may be accounted for through consideration of the steric effects imposed by the cyclohexyl groups of the chiral ligand and the stereoelectronic requirements of the elimination reaction.