(5S,7R,8R)-(-)-5,6,7,8,-tetrahydro-6,6,8-trimethyl-2-(pyridin-2-yl)-5,7-methanoquinoline | 172031-76-4

• 分子结构分类: 有机化合物 - 有机杂环化合物 - 吡啶及其衍生物
• 英文名称: (5S,7R,8R)-(-)-5,6,7,8,-tetrahydro-6,6,8-trimethyl-2-(pyridin-2-yl)-5,7-methanoquinoline
• 英文别名: (-)-5,6-Pinene bipyridine；(1R,8S,9R)-8,10,10-trimethyl-5-pyridin-2-yl-6-azatricyclo[7.1.1.02,7]undeca-2(7),3,5-triene
• CAS: 172031-76-4
• 化学式: C₁₈H₂₀N₂
• 分子量: 264.37
• InChiKey: SQOMZXUVLIOAJU-YUTCNCBUSA-N

物化性质

• 沸点：
  390.4±42.0 °C(Predicted)
• 密度：
  1.078±0.06 g/cm3(Predicted)

计算性质

• 辛醇/水分配系数(LogP)：
  3.7
• 重原子数：
  20
• 可旋转键数：
  1
• 环数：
  5.0
• sp3杂化的碳原子比例：
  0.44
• 拓扑面积：
  25.8
• 氢给体数：
  0
• 氢受体数：
  2

反应信息

• 作为反应物：
  描述：

  (5S,7R,8R)-(-)-5,6,7,8,-tetrahydro-6,6,8-trimethyl-2-(pyridin-2-yl)-5,7-methanoquinoline 、 1,2-二溴苯 在 lithium diisopropyl amide 作用下， 以 四氢呋喃 、 正己烷 为溶剂， 反应 3.0h， 以75%的产率得到(1R,8S,9R)-8-[[2-[[(1R,8S,9R)-10,10-dimethyl-5-pyridin-2-yl-6-azatricyclo[7.1.1.02,7]undeca-2(7),3,5-trien-8-yl]methyl]phenyl]methyl]-10,10-dimethyl-5-pyridin-2-yl-6-azatricyclo[7.1.1.02,7]undeca-2(7),3,5-triene
  参考文献：
  名称：

  Self-Assembly of Multinuclear Coordination Species with Chiral Bipyridine Ligands: Silver Complexes of 5,6-CHIRAGEN(o,m,p-xylidene) Ligands and Equilibrium Behaviour in Solution

  摘要：

  The complexation reactions between Ag+ and a series of enantiopure ligands belonging to the CHIRAGEN (from CHIRAlity GENerator) family (L1, L2, L3, based on (-)-5,6-pinene bipyridine) have been studied in solution. It has been shown that the length of the bridge plays a fundamental role in the self-assembly processes leading to different compounds: mononuclear complexes (with L3), mixtures of polynuclear complexes (with L2) and circular helicates (with L1). although the absolute configuration of the chiral centres ill all three ligands is the same, the metal-centred chirality of L3 (Delta) is inverted with respect to that in the other two complexes with L1 and L2 (Delta). The metal configuration is thus opposite in the mononuclear complex with respect to the polynuclear species. Detailed thermodynamic studies were carried out for the Ag+ and LI ligand system by H-1 and Ag-109 NMR spectroscopy (as a Function of concentration, temperature and pressure). At low temperature and high pressure, the [Ag(6)L1(6)](6+) hexa-nuclear circular helicate forms a tetranuclear circular helicate [Ag(4)L1(4)](4+); 2[Ag(6)L1(6)](6+)=(3)[Ag(4)L1(4)](4+). The thermodynamics parameters, obtained by temperature and pressure variation, have the following values: K-298 = (8.7 +/- 0.7) x 10(-5) mol kg(-1), DeltaH(o) = -15.65 +/- 0.8 kJ mol(-1), DeltaS(o) = -130.2 +/- 3 J mol(-1) K-1 and DeltaV(0)(256 K) = -160 +/- 12 cm(3)mol(-1). The reaction volume calculated according to Connolly's method indicates that the calculated structure of [Ag4L1(4)](4+) is plausible. Both the signs and large magnitudes of DeltaS(o) and DeltaV(o) are counterintuitive, yet can be understood by modelling methods.

  DOI：

  10.1002/1521-3765(20010119)7:2<533::aid-chem533>3.0.co;2-q
• 作为产物：
  描述：

  (+)-5,6-pinene-bipyridine 、 碘甲烷 在 lithium diisopropyl amide 作用下， 以 四氢呋喃 、 正己烷 为溶剂， 反应 2.0h， 生成 (5S,7R,8R)-(-)-5,6,7,8,-tetrahydro-6,6,8-trimethyl-2-(pyridin-2-yl)-5,7-methanoquinoline
  参考文献：
  名称：

  Enantioselective catalytic cyclopropanation of styrenes by copper complexes with chiral pinene-[5,6]-bipyridine ligands

  摘要：

  Substituted mono- and bis-pinene-[5,6]-bipyridines are useful ligands in asymmetric copper-catalyzed cyclopropanation by styrenes. Copper complexes were prepared either in situ or prior to the reaction. The catalytic reaction of styrene with ethyl diazoacetate and Cu-11b yields ethyl trans-phenylcyclopropane carboxylate in >99% yield and 87% e.e. at 0 degreesC. The corresponding cis-configured cyclopropane was produced with an e.e. of 90%. The cis/trans ratio is 22:78. Other ligands of this series are less effective, Various olefins were tested as substrates but exo-methylene olefins show the best results. (C) 2000 Elsevier Science Ltd. All rights reserved.

  DOI：

  10.1016/s0957-4166(00)00401-8

文献信息

• Synthesis of New Chiral 2,2‘-Bipyridyl-Type Ligands, Their Coordination to Molybdenum(0), Copper(II), and Palladium(II), and Application in Asymmetric Allylic Substitution, Allylic Oxidation, and Cyclopropanation
  作者：Andrei V. Malkov、Ian R. Baxendale、Marco Bella、Vratislav Langer、John Fawcett、David R. Russell、Darren J. Mansfield、Marian Valko、Pavel Kočovský

  DOI：10.1021/om000850n

  日期：2001.2.1

  of these ligands with molybdenum(0) (38−40) and copper(II) (41) have been characterized by single-crystal X-ray crystallography. While complex 38 exhibits polymorphism (monoclinic and tetragonal forms crystallize from the same batch), 41 is characterized by a tetrahedrally distorted geometry of the metal coordination. The Mo and Pd complexes exhibit modest asymmetric induction in allylic substitution

  一系列手性联吡啶基型配体的5 - 12已被合成的吡啶环的通过从头构造。的配位体的手性基团从单萜境界起源，即，松香芹酮（13 → 6，7，和9），myrtenal（18 → 5），诺蒎酮（21 → 8和10），薄荷酮（28 → 11和12）; 前三个前体可以一步一步分别从β-and烯和α-PIne烯获得。这些配体的配合物的钼（0）（38 -40）和铜（II）（41）已经通过单晶X射线晶体学表征。配合物38表现出多态性（单斜晶和四方晶从同一批中结晶出来），而复合物41的特征是金属配位体呈四面体扭曲的几何形状。Mo和Pd配合物在烯丙基取代中表现出适度的不对称诱导（43 → 44），并且从10（PINDY）和Cu（OTf）2衍生的41的Cu（I）对应物显示出良好的对映选择性（49-75％ee ）和环烯烃的烯丙基氧化反应速率（室温下≥30分钟）（47 →48）。11（MINDY）的Cu（I）络合物在ee高达72％的环丙烷化（49