(1R,8S,9R)-8,10,10-trimethyl-5-[6-[(1R,8S,9R)-8,10,10-trimethyl-6-azatricyclo[7.1.1.02,7]undeca-2(7),3,5-trien-5-yl]pyridin-2-yl]-6-azatricyclo[7.1.1.02,7]undeca-2(7),3,5-triene | 288089-04-3

• 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: (1R,8S,9R)-8,10,10-trimethyl-5-[6-[(1R,8S,9R)-8,10,10-trimethyl-6-azatricyclo[7.1.1.02,7]undeca-2(7),3,5-trien-5-yl]pyridin-2-yl]-6-azatricyclo[7.1.1.02,7]undeca-2(7),3,5-triene
• CAS: 288089-04-3
• 化学式: C₃₁H₃₅N₃
• 分子量: 449.639
• InChiKey: IQILHYLAWFRLFK-RJFPACLCSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  6.5
• 重原子数：
  34
• 可旋转键数：
  2
• 环数：
  9.0
• sp3杂化的碳原子比例：
  0.52
• 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：

  (1R,8S,9R)-8,10,10-trimethyl-5-[6-[(1R,8S,9R)-8,10,10-trimethyl-6-azatricyclo[7.1.1.02,7]undeca-2(7),3,5-trien-5-yl]pyridin-2-yl]-6-azatricyclo[7.1.1.02,7]undeca-2(7),3,5-triene 在 间氯过氧苯甲酸 作用下， 以 二氯甲烷 为溶剂， 反应 10.0h， 以70%的产率得到(1R,8S,9R)-8,10,10-trimethyl-6-oxido-5-[1-oxido-6-[(1R,8S,9R)-8,10,10-trimethyl-6-oxido-6-azoniatricyclo[7.1.1.02,7]undeca-2(7),3,5-trien-5-yl]pyridin-1-ium-2-yl]-6-azoniatricyclo[7.1.1.02,7]undeca-2(7),3,5-triene
  参考文献：
  名称：

  第一系列手性2,2'：6'，2''-叔吡啶三-N-氧化物配体，用于路易斯碱催化的醛的不对称烯丙基化。

  摘要：

  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％）。

  DOI：

  10.1039/b407933g
• 作为产物：
  描述：

  tpy-β-pinene 、 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， 以46%的产率得到(1R,8S,9R)-8,10,10-trimethyl-5-[6-[(1R,8S,9R)-8,10,10-trimethyl-6-azatricyclo[7.1.1.02,7]undeca-2(7),3,5-trien-5-yl]pyridin-2-yl]-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

文献信息

• 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）。
• Chiral C1-symmetric 2,2′:6′,2′′-terpyridine ligands: Synthesis, characterization, complexation with copper(II), rhodium(III) and ruthenium(II) ions and use of the complexes in catalytic cyclopropanation of styrene
  作者：Chi-Tung Yeung、Wing-Sze Lee、Chui-Shan Tsang、Shek-Man Yiu、Wing-Tak Wong、Wai-Yeung Wong、Hoi-Lun Kwong

  DOI：10.1016/j.poly.2010.01.017

  日期：2010.3

  copper(II) complexes, of formula [Cu(L)Cl2], the rhodium(III) complexes, of formula [Rh(L)Cl3], and the ruthenium(II) complexes, of formula cis- or trans-[Ru(L)(X)Cl2] (X = DMSO or CO), were synthesized. Structures of a chiral C1-ligand, a copper complex, a rhodium complex and a ruthenium DMSO complex were analysed using X-ray crystal structure analysis. The copper, rhodium and ruthenium complexes were

  摘要制备了三个新的光学纯的C1-吡啶配体（L1-3），式[Cu（L）Cl2]的铜（II）配合物，式[Rh（L）Cl3]的铑（III）配合物，并合成了具有顺式或反式[Ru（L）（X）Cl2]（X = DMSO或CO）的钌（II）配合物。使用X射线晶体结构分析来分析手性C 1配体，铜配合物，铑配合物和钌DMSO配合物的结构。铜，铑和钌配合物被证明是环丙烷化催化剂的前体。[Cu（L）Cl2]，[Rh（L）Cl3]或顺式或反式[Ru（L）（X）Cl2]与AgOTf的反应将络合物转化为催化剂，在反式[Ru]的情况下（L）（CO）Cl2]对苯乙烯环丙烷与重氮乙酸叔丁酯的顺式异构体的对映选择性高达67％ee。与铜的C2-类似物的比较，
• 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。
• Zinc(II) complex of terpyridine-crown macrocycle: A new motif in fluorescence sensing of zwitterionic amino acids
  作者：Hoi-Lun Kwong、Wing-Leung Wong、Chi-Sing Lee、Chi-Tung Yeung、Pang-Fei Teng

  DOI：10.1016/j.inoche.2009.06.013

  日期：2009.9

  Abstract A new fluorescence macrocyclic receptor based on the Zn(II) complex of a C 2 -terpyridine and a crown ether has been developed for molecular recognition of zwitterionic amino acids in water/DMF solution with remarkable selectivity towards l -aspartate ( K = 4.5 × 10 4 M −1 ) and l -cysteine ( K = 2.5 × 10 4 M −1 ).

  摘要 基于 C 2 -三联吡啶和冠醚的 Zn(II) 复合物开发了一种新型荧光大环受体，用于分子识别水/DMF 溶液中的两性离子氨基酸，对 l-天冬氨酸 (K = 4.5) 具有显着的选择性× 10 4 M -1 ) 和 l -半胱氨酸 (K = 2.5 × 10 4 M -1 )。
• 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
  作者：Hoi-Lun Kwong、Wing-Leung Wong、Wing-Sze Lee、Leung-Shi Cheng、Wing-Tak Wong

  DOI：10.1016/s0957-4166(01)00431-1

  日期：2001.10

  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.