(1R,8S)-1,11,11-trimethyl-4-[6-[(1R,8S)-1,11,11-trimethyl-3-azatricyclo[6.2.1.02,7]undeca-2(7),3,5-trien-4-yl]pyridin-2-yl]-3-azatricyclo[6.2.1.02,7]undeca-2(7),3,5-triene | 412929-59-0

• 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: (1R,8S)-1,11,11-trimethyl-4-[6-[(1R,8S)-1,11,11-trimethyl-3-azatricyclo[6.2.1.02,7]undeca-2(7),3,5-trien-4-yl]pyridin-2-yl]-3-azatricyclo[6.2.1.02,7]undeca-2(7),3,5-triene
• CAS: 412929-59-0
• 化学式: C₃₁H₃₅N₃
• 分子量: 449.639
• InChiKey: HNODJDMNLPXDLI-VJWQHVNVSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  6.8
• 重原子数：
  34
• 可旋转键数：
  2
• 环数：
  7.0
• 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)-1,11,11-trimethyl-4-[6-[(1R,8S)-1,11,11-trimethyl-3-azatricyclo[6.2.1.02,7]undeca-2(7),3,5-trien-4-yl]pyridin-2-yl]-3-azatricyclo[6.2.1.02,7]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 8.0h， 以40%的产率得到(1R,8S)-1,11,11-Trimethyl-4-[6-((1R,8S)-1,11,11-trimethyl-3-aza-tricyclo[6.2.1.0^2,7]undeca-2,4,6-trien-4-yl)-pyridin-2-yl]-3-aza-tricyclo[6.2.1.0^2,7]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：

  <1R-(1β,4β)>-3-methylene-1,7,7-trimethylbicyclo<2.2.1>heptan-2-one 、 N,N'-<2,2'-(Pyridine-2,6-diyl)bis(2-oxoethyl)>bis(pyridinium iodide) 在 ammonium acetate 作用下， 以 溶剂黄146 为溶剂， 以37%的产率得到(1R,8S)-1,11,11-trimethyl-4-[6-[(1R,8S)-1,11,11-trimethyl-3-azatricyclo[6.2.1.02,7]undeca-2(7),3,5-trien-4-yl]pyridin-2-yl]-3-azatricyclo[6.2.1.02,7]undeca-2(7),3,5-triene
  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

• 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.
• Synthesis of new chiral terpyridine mono-N-oxide and di-N-oxide ligands and their applications in copper-catalyzed asymmetric cyclopropanation
  作者：Wing-Leung Wong、Wing-Sze Lee、Hoi-Lun Kwong

  DOI：10.1016/s0957-4166(02)00270-7

  日期：2002.8

  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.