tpy-β-pinene | 223441-00-7

• 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: tpy-β-pinene
• 英文别名: (1R,9R)-5-[6-[(1R,9R)-10,10-dimethyl-6-azatricyclo[7.1.1.02,7]undeca-2(7),3,5-trien-5-yl]pyridin-2-yl]-10,10-dimethyl-6-azatricyclo[7.1.1.02,7]undeca-2(7),3,5-triene
• CAS: 223441-00-7
• 化学式: C₂₉H₃₁N₃
• 分子量: 421.585
• InChiKey: YSIUULOXDZKPSE-JYWFKMLOSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  5.9
• 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：

  苄基碘 、 tpy-β-pinene 在 lithium diisopropyl amide 作用下， 以 四氢呋喃 、 正己烷 为溶剂， 反应 2.0h， 以39%的产率得到(1R,8S,9R)-8-benzyl-5-[6-[(1R,8S,9R)-8-benzyl-10,10-dimethyl-6-azatricyclo[7.1.1.02,7]undeca-2(7),3,5-trien-5-yl]pyridin-2-yl]-10,10-dimethyl-6-azatricyclo[7.1.1.02,7]undeca-2(7),3,5-triene
  参考文献：
  名称：

  First enantioselective catalyst based on a chiral terpyridine: synthesis of new C2-symmetric 2,2′:6′,2′′-terpyridine ligands and copper-catalyzed enantioselective cyclopropanation of alkenes

  摘要：

  New C-2-symmetric chiral 2,2':6',2 "-terpyridines were prepared from readily available homochiral materials. Copper complexes of these ligands were prepared in situ and their catalytic activities in cyclopropanations of alkenes with alkyl diazoacetate to give cyclopropyl esters were studied. In all cases, the cyclopropyl ester yields were excellent and enantioselectivities up to 94% ee were observed. Competition experiments revealed that electron-donating substituents on styrene accelerate the reaction. A Hammett plot exhibited a good linearity with a negative rho(+) value (-0.79). (C) 2000 Elsevier Science Ltd. All rights reserved.

  DOI：

  10.1016/s0957-4166(00)00182-8
• 作为产物：
  描述：

  pinocarvone 、 N,N'-<2,2'-(Pyridine-2,6-diyl)bis(2-oxoethyl)>bis(pyridinium iodide) 在 乙酸铵 、 溶剂黄146 作用下， 以59%的产率得到tpy-β-pinene
  参考文献：
  名称：

  First enantioselective catalyst based on a chiral terpyridine: synthesis of new C2-symmetric 2,2′:6′,2′′-terpyridine ligands and copper-catalyzed enantioselective cyclopropanation of alkenes

  摘要：

  New C-2-symmetric chiral 2,2':6',2 "-terpyridines were prepared from readily available homochiral materials. Copper complexes of these ligands were prepared in situ and their catalytic activities in cyclopropanations of alkenes with alkyl diazoacetate to give cyclopropyl esters were studied. In all cases, the cyclopropyl ester yields were excellent and enantioselectivities up to 94% ee were observed. Competition experiments revealed that electron-donating substituents on styrene accelerate the reaction. A Hammett plot exhibited a good linearity with a negative rho(+) value (-0.79). (C) 2000 Elsevier Science Ltd. All rights reserved.

  DOI：

  10.1016/s0957-4166(00)00182-8

文献信息

• Process for the ruthenium-catalysed epoxidation of olefins by means of hydrogen peroxide
  申请人：Magerlein Wolfgang

  公开号：US20060161011A1

  公开（公告）日：2006-07-20

  The present invention relates to a process for the epoxidation of olefins using catalysts based on ruthenium complexes in the presence of hydrogen peroxide.

  本发明涉及一种利用基于钌配合物的催化剂在过氧化氢存在下对烯烃进行环氧化的方法。
• Catalytic and asymmetric cyclopropanation of alkenes catalysed by rhenium(i) bipyridine and terpyridine tricarbonyl complexes
  作者：Chi-Tung Yeung、Pang-Fei Teng、Ho-Lun Yeung、Wing-Tak Wong、Hoi-Lun Kwong

  DOI：10.1039/b712995e

  日期：——

  Re(I) tricarbonyl bipyridine and terpyridine complexes catalyse stereospecific cyclopropanation of alkenes; high selectivity of cyclopropane vs coupling and an ee of 73% and 62% for cis- and trans-cyclopropanes of styrene respectively were achieved with the [Re(L)(CO)(3)(MeCN)]OTf complex (L = chiral C(2)-symmetric terpyridine ligand).

  Re（I）三羰基联吡啶和三联吡啶配合物催化烯烃的立体有规环丙烷化；[Re（L）（CO）（3）（MeCN）] OTf配合物（L =手性）可实现较高的环丙烷相对于偶联的选择性以及对苯乙烯的顺式和反式环丙烷的ee分别为73％和62％ C（2）-对称的吡啶吡啶配体）。
• 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。
• Ziegler, Marco; Monney, Veronique; Stoeckli-Evans, Helen, Journal of the Chemical Society, Dalton Transactions, 1999, p. 667 - 676
  作者：Ziegler, Marco、Monney, Veronique、Stoeckli-Evans, Helen、Zelewsky, Alex Von、Sasaki, Isabelle、et al.

  DOI：——

  日期：——
• Enantiopure terdentate N-donor ligands and their Fe(II) and Co(II) complexes
  作者：Dominique Suhr、Didier Lötscher、Helen Stoeckli-Evans、Alex von Zelewsky

  DOI：10.1016/s0020-1693(02)01204-5

  日期：2002.12

  A series of Fe(II) and Co(II) complexes with two chiral terpy ligands (L2, L3, L4 and L5) and a related pyridine-diimine (L6) have been prepared and structurally characterized. In all cases except one, the metals are five coordinated with an approximately trigonal-bipyramidal coordination sphere. The two lateral N-donor atoms occupy the apical positions. The only exception is complex 5 (CoL4Cl(2)), where one lateral N-donor interacts only weakly with the metal (2.63 vs. 2.21 Angstrom) forming thus a nearly tetrahedral coordination sphere. U and L6 were also structurally characterized. They show the expected transoid arrangement of the donor atoms. (C) 2002 Elsevier Science B.V. All rights reserved.