(6S,8S)-2,6-bis(7,7-dimethyl-5,6,7,8-tetrahydro-6,8-methanoquinolin-2-yl)pyridine | 389086-98-0

• 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: (6S,8S)-2,6-bis(7,7-dimethyl-5,6,7,8-tetrahydro-6,8-methanoquinolin-2-yl)pyridine
• 英文别名: (1R,9R)-4-[6-[(1R,9R)-10,10-dimethyl-3-azatricyclo[7.1.1.02,7]undeca-2(7),3,5-trien-4-yl]pyridin-2-yl]-10,10-dimethyl-3-azatricyclo[7.1.1.02,7]undeca-2(7),3,5-triene
• CAS: 389086-98-0
• 化学式: C₂₉H₃₁N₃
• 分子量: 421.585
• InChiKey: XIZJGVDDWYAADR-TUFLPTIASA-N

计算性质

• 辛醇/水分配系数(LogP)：
  5.5
• 重原子数：
  32
• 可旋转键数：
  2
• 环数：
  9.0
• sp3杂化的碳原子比例：
  0.48
• 拓扑面积：
  38.7
• 氢给体数：
  0
• 氢受体数：
  3

反应信息

• 作为反应物：
  描述：

  (6S,8S)-2,6-bis(7,7-dimethyl-5,6,7,8-tetrahydro-6,8-methanoquinolin-2-yl)pyridine 在 间氯过氧苯甲酸 作用下， 以 二氯甲烷 为溶剂， 反应 2.0h， 以30%的产率得到(1R,9R)-4-[6-((1R,9R)-10,10-Dimethyl-3-aza-tricyclo[7.1.1.0^2,7]undeca-2,4,6-trien-4-yl)-pyridin-2-yl]-10,10-dimethyl-3-aza-tricyclo[7.1.1.0^2,7]undeca-2,4,6-triene 3-oxide
  参考文献：
  名称：

  Synthesis of new chiral terpyridine mono-N-oxide and di-N-oxide ligands and their applications in copper-catalyzed asymmetric cyclopropanation

  摘要：

  New families of chiral terpyridine mono-N-oxides L-1-L-3 and di-N-oxides L-4-L-6, were synthesized in moderate to good yields by simple oxidation of their corresponding terpyridines with m-CPBA. The copper(II) triflate complexes of these ligands were found to be highly effective catalysts for asymmetric cyclopropanation of styrene with ethyl diazoacetate. The isolated yields of cyclopropane were excellent and the enantiomeric excesses of up to 83% were observed. Competition experiments with substituted styrenes showed good sigma(+) correlations with rho = -0.70 for mono-N-oxide L-3 and rho = -0.69 for di-N-oxide L-6. (C) 2002 Elsevier Science Ltd. All rights reserved.

  DOI：

  10.1016/s0957-4166(02)00270-7
• 作为产物：
  描述：

  N,N'-<2,2'-(Pyridine-2,6-diyl)bis(2-oxoethyl)>bis(pyridinium iodide) 、 (1R,5R)-6,6-dimethyl-3-methylenebicyclo[3.1.1]heptan-2-one 在 ammonium acetate 作用下， 以 溶剂黄146 为溶剂， 以60%的产率得到(6S,8S)-2,6-bis(7,7-dimethyl-5,6,7,8-tetrahydro-6,8-methanoquinolin-2-yl)pyridine
  参考文献：
  名称：

  New chiral 2,2′:6′,2″-terpyridine ligands from the chiral pool: synthesis, crystal structure of a rhodium complex and uses in copper- and rhodium-catalyzed enantioselective cyclopropanation of styrene

  摘要：

  A number of chiral G-symmetric 2,2':6'.2 " terpyridines L-1-L-4 were synthesized in moderate to good yields from commercially available chiral materials. Copper(II) and rhodium(Ill) chloride complexes of these ligands were prepared in good yields. The Rh(L-2)Cl-3 complex was isolated as a yellow crystalline solid and characterized by X-ray crystallography. Both Cu(L)(OTf)(2) and Rh(L)(OTf)(3) were found to be active catalysts in the cyclopropanation of styrene with ethyl diazoacetate. Enantioselectivity up to 82% e.e. was observed. (C) 2001 Elsevier Science Ltd. All rights reserved.

  DOI：

  10.1016/s0957-4166(01)00431-1

文献信息

• The first series of chiral 2,2′:6′,2″-terpyridine tri-N-oxide ligands for Lewis base-catalyzed asymmetric allylation of aldehydes
  作者：Wing-Leung Wong、Chi-Sing Lee、Hon-Kit Leung、Hoi-Lun Kwong

  DOI：10.1039/b407933g

  日期：——

  The first series of chiral 2,2':6',2''-terpyridine tri-N-oxide ligands have been developed; They were showed to be active Lewis base-catalysts for asymmetric allylation of aldehydes using allyltrichlorosilane with optimal results at 0 degrees C for electron-deficient aromatic aldehydes (yields up to 97% and enantioselectivities up to 86% ee).

  已开发出第一个手性2,2'：6'，2''-叔吡啶三-N-氧化物配体。它们被证明是使用烯丙基三氯硅烷进行醛的不对称烯丙基化的活性路易斯碱催化剂，对于缺电子的芳族醛，其在0℃的最佳结果（产率高达97％，对映选择性高达ee的86％）。
• Cobalt and iron complexes of chiral C1- and C2-terpyridines: Synthesis, characterization and use in catalytic asymmetric cyclopropanation of styrenes
  作者：Chi-Tung Yeung、Kiu-Chor Sham、Wing-Sze Lee、Wing-Tak Wong、Wai-Yeung Wong、Hoi-Lun Kwong

  DOI：10.1016/j.ica.2009.02.034

  日期：2009.7

  2 -terpyridine ligands ( L ) form cobalt(II) and iron(II) complexes of formula [Co( L )Cl 2 ] and [Fe( L )Cl 2 ], respectively, and Iron(III) complexes of formulas [Fe( L )Cl 3 ]. Structures of three new chiral cobalt(II) and one iron(III) complexes were analysed using X-ray crystal structure analysis. These complexes were shown to be precursor of efficient catalyst for cyclopropanation. Reaction with

  光学纯的C 1-和C 2-吡啶吡啶配体（L）分别形成式[Co（L）Cl 2]和[Fe（L）Cl 2]的钴（II）和铁（II）配合物，以及铁（ III）式[Fe（L）Cl 3]的配合物。使用X射线晶体结构分析了三种新的手性钴（II）和一种铁（III）配合物的结构。这些络合物被证明是有效的环丙烷化催化剂的前体。与AgOTf的反应将络合物转化为活性催化剂，与重氮乙酸乙酯一起，苯乙烯环丙烷的反式异构体的对映选择性高达76％ee，顺式异构体的对映选择性高达83％ee。Hammett研究表明，钴和铁配合物的活性物种均与σp常数呈非线性关系。
• First Example of Supported Microwave-Assisted Synthesis of New Chiral Bipyridines and a Terpyridine − Use in Asymmetric Cyclopropanation
  作者：Frédéric Pezet、Isabelle Sasaki、Jean-Claude Daran、Jérôme Hydrio、Hassan Aït-Haddou、Gilbert Balavoine

  DOI：10.1002/1099-0682(200109)2001:10<2669::aid-ejic2669>3.0.co;2-y

  日期：2001.9
• Cyclopropanation of styrene with diazoacetates catalyzed by copper and rhodium complexes of new chiral 2,2′:6′,2″-terpyridines derived from natural occurring compounds
  作者：Giorgio Chelucci、Antonio Saba、Franco Soccolini、Davide Vignola

  DOI：10.1016/s1381-1169(01)00287-4

  日期：2002.1

  Three new chiral 2,2': 6',2"-terpyridines (terpy) were prepared from (-)-beta-pinene, (+)-camphor and (+)-2-carene and the corresponding copper and rhodium complexes were assessed as chiral catalysts for the enantioselective cyclopropanation of styrene with diazoacetates. Enantioselectivities up to 64% were obtained. (C) 2002 Elsevier Science B.V. All rights reserved.