(+)-hydrocinchonine

• 分子结构分类: 有机化合物 - 生物碱及其衍生物 - 金鸡纳生物碱
• 英文名称: (+)-hydrocinchonine
• 英文别名: (S)-[(2R,4S,5S)-5-ethyl-1-azabicyclo[2.2.2]octan-2-yl]-quinolin-4-ylmethanol
• 化学式: C₁₉H₂₄N₂O
• 分子量: 296.412
• InChiKey: WFJNHVWTKZUUTR-CFGMGRTJSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  2.9
• 重原子数：
  22
• 可旋转键数：
  3
• 环数：
  5.0
• sp3杂化的碳原子比例：
  0.53
• 拓扑面积：
  36.4
• 氢给体数：
  1
• 氢受体数：
  3

反应信息

• 作为反应物：
  描述：

  tppts 、 (+)-hydrocinchonine 以 甲醇 、 二氯甲烷 为溶剂， 以91%的产率得到
  参考文献：
  名称：

  Rhodium complexes with chiral counterions: achiral catalysts in chiral matrices

  摘要：

  The neutral complexes [Rh(I)(NBD)((1S)-10-camphorsulfonate)] (2) and [Rh(I)((R)-N-acetylphenylalanate)] (4) reacted with bis(diphenylphosphino)ethane (dppe) to form the cationic Rh(1)(NBD)(dppe) complexes, 5 and 6, respectively, accompanied by their corresponding chiral counteranions. Analogously, 4 reacted with 4,4'-dimethylbipyridine to yield complex 7. Complexes 5 and 6 disproportionated in aprotic solvents to form the corresponding bis-diphosphine complexes 8 and 9, respectively. 8 was characterized by an X-ray crystal structure analysis. In order to form achiral Rh(I) complexes bearing chiral countercations new sulfonated monophosphines 13-16 with chiral ammonium cations were synthesized. Tris-triphenylphosphinosulfonic acid (H3TPPS, 11) was used to protonate chiral amines to yield chiral ammonium phosphines 14-16. Thallium-tris-triphenylphosphinosulfonate (Tl3TPPS, 12) underwent metathesis with a chiral quartenary ammonium iodide to yield the proton free chiral ammonium phosphine 13. Phosphines 15 and 16 reacted with [Rh(NBD)(2)]BF4 to afford the highly charged chiral zwitterionic complexes [Rh(NBD)(TPPS)(2)][(R)-N,N-dimethyl-1-(naphtyl)ethylammonium](5) (17) and [Rh(NBD)(TPPS)(2)][BF4][(R)-NN-dimethyl-phenethylammonium](6) (18), respectively. Complexes 5, 6, and 18 were tested as precatalysts for the hydrogenation of de-hydro-N-acetylphenylalanine (19) and methyl-(Z)-(alpha)-acetoamidocinnamate (MAC, 20) under homogeneous and heterogeneous (silica-supported and self-supported) conditions. None of the reactions was enantioselective. (C) 2003 Elsevier B.V. All rights reserved.

  DOI：

  10.1016/j.jorganchem.2003.12.012

文献信息

• Highly Enantioselective and Practical Cinchona-Derived Phase-Transfer Catalysts for the Synthesis of α-Amino Acids This work was supported by grants from Aminogen Co. (Korea) through the Research Center of New Drug Development of Seoul National University and the Research Institute of Pharmaceutical Sciences in the College of Pharmacy of Seoul National University.
  作者：Hyeung-geun Park、Byeong-Seon Jeong、Mi-Sook Yoo、Jeong-Hee Lee、Mi-kyoung Park、Yeon-Ju Lee、Mi-Jeong Kim、Sang-sup Jew

  DOI：10.1002/1521-3773(20020816)41:16<3036::aid-anie3036>3.0.co;2-3

  日期：2002.8.16
• Organocatalytic Asymmetric Synthesis of Versatile γ-Lactams
  作者：Thomas B. Poulsen、Gustav Dickmeiss、Jacob Overgaard、Karl Anker Jørgensen

  DOI：10.1002/anie.200800329

  日期：2008.6.9
• JANCZEWSKI, M.;JANOWSKI, W., ANN. UMCS, 1976XXXX1977X0X0, 31-32, 333-354
  作者：JANCZEWSKI, M.、JANOWSKI, W.

  DOI：——

  日期：——
• Rhodium complexes with chiral counterions: achiral catalysts in chiral matrices
  作者：Romano Dorta、Linda Shimon、David Milstein

  DOI：10.1016/j.jorganchem.2003.12.012

  日期：2004.2

  The neutral complexes [Rh(I)(NBD)((1S)-10-camphorsulfonate)] (2) and [Rh(I)((R)-N-acetylphenylalanate)] (4) reacted with bis(diphenylphosphino)ethane (dppe) to form the cationic Rh(1)(NBD)(dppe) complexes, 5 and 6, respectively, accompanied by their corresponding chiral counteranions. Analogously, 4 reacted with 4,4'-dimethylbipyridine to yield complex 7. Complexes 5 and 6 disproportionated in aprotic solvents to form the corresponding bis-diphosphine complexes 8 and 9, respectively. 8 was characterized by an X-ray crystal structure analysis. In order to form achiral Rh(I) complexes bearing chiral countercations new sulfonated monophosphines 13-16 with chiral ammonium cations were synthesized. Tris-triphenylphosphinosulfonic acid (H3TPPS, 11) was used to protonate chiral amines to yield chiral ammonium phosphines 14-16. Thallium-tris-triphenylphosphinosulfonate (Tl3TPPS, 12) underwent metathesis with a chiral quartenary ammonium iodide to yield the proton free chiral ammonium phosphine 13. Phosphines 15 and 16 reacted with [Rh(NBD)(2)]BF4 to afford the highly charged chiral zwitterionic complexes [Rh(NBD)(TPPS)(2)][(R)-N,N-dimethyl-1-(naphtyl)ethylammonium](5) (17) and [Rh(NBD)(TPPS)(2)][BF4][(R)-NN-dimethyl-phenethylammonium](6) (18), respectively. Complexes 5, 6, and 18 were tested as precatalysts for the hydrogenation of de-hydro-N-acetylphenylalanine (19) and methyl-(Z)-(alpha)-acetoamidocinnamate (MAC, 20) under homogeneous and heterogeneous (silica-supported and self-supported) conditions. None of the reactions was enantioselective. (C) 2003 Elsevier B.V. All rights reserved.