(1S,3R,5R,6S,8R,10R,11S,13R,15R,16S,18R,20R,21S,23R,25R,26S,28R,30R,31S,33R,35R,36R,37R,38R,39R,40R,41R,42R,43R,44R,45R,46R,47R,48R,49R)-5,10,15,20,25,30-hexakis(hydroxymethyl)-35-[(3-hydroxypropylamino)methyl]-2,4,7,9,12,14,17,19,22,24,27,29,32,34-tetradecaoxaoctacyclo[31.2.2.23,6.28,11.213,16.218,21.223,26.228,31]nonatetracontane-36,37,38,39,40,41,42,43,44,45,46,47,48,49-tetradecol | 781643-12-7

• 分子结构分类: 有机化合物 - 有机氧化合物
• 英文名称: (1S,3R,5R,6S,8R,10R,11S,13R,15R,16S,18R,20R,21S,23R,25R,26S,28R,30R,31S,33R,35R,36R,37R,38R,39R,40R,41R,42R,43R,44R,45R,46R,47R,48R,49R)-5,10,15,20,25,30-hexakis(hydroxymethyl)-35-[(3-hydroxypropylamino)methyl]-2,4,7,9,12,14,17,19,22,24,27,29,32,34-tetradecaoxaoctacyclo[31.2.2.23,6.28,11.213,16.218,21.223,26.228,31]nonatetracontane-36,37,38,39,40,41,42,43,44,45,46,47,48,49-tetradecol
• CAS: 781643-12-7
• 化学式: C₄₅H₇₇NO₃₅
• 分子量: 1192.09
• InChiKey: YXAPGPIXYHYBLX-HCHLQLBUSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  -15.1
• 重原子数：
  81
• 可旋转键数：
  11
• 环数：
  21.0
• sp3杂化的碳原子比例：
  1.0
• 拓扑面积：
  566
• 氢给体数：
  22
• 氢受体数：
  36

反应信息

• 作为产物：
  描述：

  3-氨基-1-丙醇 、 mono-6-deoxy-6-(p-toluenesulfonyl)-β-cyclodextrin 反应 12.0h， 以55.48%的产率得到(1S,3R,5R,6S,8R,10R,11S,13R,15R,16S,18R,20R,21S,23R,25R,26S,28R,30R,31S,33R,35R,36R,37R,38R,39R,40R,41R,42R,43R,44R,45R,46R,47R,48R,49R)-5,10,15,20,25,30-hexakis(hydroxymethyl)-35-[(3-hydroxypropylamino)methyl]-2,4,7,9,12,14,17,19,22,24,27,29,32,34-tetradecaoxaoctacyclo[31.2.2.23,6.28,11.213,16.218,21.223,26.228,31]nonatetracontane-36,37,38,39,40,41,42,43,44,45,46,47,48,49-tetradecol
  参考文献：
  名称：

  Cyclodextrin–[RuCl2(Arene)]2 conjugates: another way to enhance the enantioselectivity of aromatic ketones reduction by aromatic ligands' volume

  摘要：

  Eight amino alcohol-modified beta-CDs CD-1-CD-8 have been synthesized in acceptable yields and were employed to form artificial metalloenzymes with [RuCl2(Benzene)](2) and [RuCl2(Mesitylene)](2), respectively. All the conformations of CD-1 CD-8, the complexes between CD-1 CD-8 and [RuCl2(Arene)](2), and the inclusion complexes between CD-1 CD-8 and acetophenone were characterized by UV, H-1 NMR, H-1 ROESY NMR, and quantum calculation. The catalytic activity of the formed artificial metalloenzymes in the asymmetric hydrogenation of aromatic ketones, especially the effect of the aromatic ligands' volume on the enantioselectivity were investigated in detail, in which it was obvious that the enantioselectivity increased as the increase in the aromatic ligands' volume. For the best artificial metalloenzyme constructed from the complex between CD-8 and [Rucl(2)(Mesitylene)](2), which not only exhibits a good tolerance to a wide range of substrates but also demonstrates some substrate selectivity, 76.39% ee was obtained for acetophenone and 79.67% ee for 2-acetylnaphthalene. A strategy to improve the enantioselectivity in the asymmetric reactions catalyzed by the artificial metalloenzymes based on CDs has been provided. (C) 2013 Elsevier Ltd. All rights reserved.

  DOI：

  10.1016/j.tet.2013.07.077

文献信息

• Amino alcohol-modified β-cyclodextrin inducing biomimetic asymmetric oxidation of thioanisole in water
  作者：Hai-Min Shen、Hong-Bing Ji

  DOI：10.1016/j.carres.2012.03.034

  日期：2012.6

  Inspired by beta-CD, a macrocyclic oligomers of D-(+)-glucopyranose and a renewable material, which could be obtained from starch, that can promote a lot of organic reactions in water, a green solvent, several amino alcohol-modified beta-CDs CD-1 to CD-7 were synthesized in the yields of 36-61%. Their conformations in vacuum and in aqueous solution were optimized by quantum calculation. Their complexes with sodium molybdate prepared in situ were characterized by H-1 NMR and were applied in the asymmetric oxidation of thioanisole. Their performance in inducing enantioselectivity was investigated in detail. For the optimal one, CD-1, moderate enantioselectivity (56% ee) was achieved in aqueous CH3COONa-HCl buffer solution (pH 7.0). The abilities of CD-1 to CD-7 to induce asymmetry are highly dependent on the pH value of the reaction medium and the structure of the modifying group. The origin of the moderate enantioselectivity and the reaction mechanism were investigated with the aid of H-1 ROESY NMR studies and quantum calculation. The moderate enantioselectivity was attributed to the two different binding models between CD-1 and thioanisole, which could be defined as intramolecular catalysis and intermolecular catalysis, in which intramolecular catalysis gave (S)-methyl phenyl sulfoxide and intermolecular catalysis gave (R, S)-methyl phenyl sulfoxide. (C) 2012 Elsevier Ltd. All rights reserved.
• Cyclodextrin–[RuCl2(Arene)]2 conjugates: another way to enhance the enantioselectivity of aromatic ketones reduction by aromatic ligands' volume
  作者：Hai-Min Shen、Hong-Bing Ji

  DOI：10.1016/j.tet.2013.07.077

  日期：2013.9

  Eight amino alcohol-modified beta-CDs CD-1-CD-8 have been synthesized in acceptable yields and were employed to form artificial metalloenzymes with [RuCl2(Benzene)](2) and [RuCl2(Mesitylene)](2), respectively. All the conformations of CD-1 CD-8, the complexes between CD-1 CD-8 and [RuCl2(Arene)](2), and the inclusion complexes between CD-1 CD-8 and acetophenone were characterized by UV, H-1 NMR, H-1 ROESY NMR, and quantum calculation. The catalytic activity of the formed artificial metalloenzymes in the asymmetric hydrogenation of aromatic ketones, especially the effect of the aromatic ligands' volume on the enantioselectivity were investigated in detail, in which it was obvious that the enantioselectivity increased as the increase in the aromatic ligands' volume. For the best artificial metalloenzyme constructed from the complex between CD-8 and [Rucl(2)(Mesitylene)](2), which not only exhibits a good tolerance to a wide range of substrates but also demonstrates some substrate selectivity, 76.39% ee was obtained for acetophenone and 79.67% ee for 2-acetylnaphthalene. A strategy to improve the enantioselectivity in the asymmetric reactions catalyzed by the artificial metalloenzymes based on CDs has been provided. (C) 2013 Elsevier Ltd. All rights reserved.