N-(6^A-deoxy-β-cyclodextrin-6^A-yl)-5-(aminocarbonyl)-3-(phenyl)-4,5-dihydroisoxazole

• 分子结构分类: 有机化合物 - 有机氧化合物
• 英文名称: N-(6^A-deoxy-β-cyclodextrin-6^A-yl)-5-(aminocarbonyl)-3-(phenyl)-4,5-dihydroisoxazole
• 英文别名: 3-phenyl-N-[[(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)-36,37,38,39,40,41,42,43,44,45,46,47,48,49-tetradecahydroxy-10,15,20,25,30,35-hexakis(hydroxymethyl)-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]nonatetracontan-5-yl]methyl]-4,5-dihydro-1,2-oxazole-5-carboxamide
• 化学式: C₅₂H₇₈N₂O₃₆
• 分子量: 1307.18
• InChiKey: BRJIWXJAIANHQL-JPPFGXHBSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  -13.4
• 重原子数：
  90
• 可旋转键数：
  10
• 环数：
  23.0
• sp3杂化的碳原子比例：
  0.85
• 拓扑面积：
  585
• 氢给体数：
  21
• 氢受体数：
  37

反应信息

• 作为产物：
  描述：

  benzohydroximoyl chloride 、 6-乙酰氨基-β-环糊精 在 三乙胺 作用下， 以 水 为溶剂， 反应 15.0h， 以97%的产率得到N-(6^A-deoxy-β-cyclodextrin-6^A-yl)-5-(aminocarbonyl)-3-(phenyl)-4,5-dihydroisoxazole
  参考文献：
  名称：

  β-Cyclodextrin as a Scaffold for Supramolecular Chemistry, To Reverse the Regioselectivity of Nitrile Oxide Cycloadditions

  摘要：

  beta-Cyclodextrin has been used as a molecular scaffold, whereby tethering dipolarophiles to the cyclodextrin and then allowing preassociation of the modified cyclodextrins with aromatic nitrile oxides, as host-guest complexes, controls the relative orientations of the dipoles and the dipolarophiles in their cycloadditions. In this manner it has been possible to reverse the usual regioselectivity of cycloadditions of nitrile oxides, as illustrated by reactions with a terminal alkene, a terminal alkyne, and a 1,2-disubstituted alkene. For example, iii aqueous solution, 4-tert-butylbenzonitrile oxide reacted with 6(A)-deoxy-6(A)-propynamido-beta-cyclodextrin to give the corresponding 4- and 5-substituted isoxazoles, in a 15:1 ratio. With DMF as the solvent, to reduce the extent of host-guest complexation, the product ratio was 1:1.5. The role of complexation in these reactions is also demonstrated by contrasting these results with that of the reaction of the nitrile oxide with methyl propynoate, which afforded only the 5-substituted cycloaddition product. Molecular recognition by the cyclodextrin scaffolds was demonstrated through treatment of 4-tert-butylbenzonitrile oxide with an equimolar mixture of 6(A)-deoxy-6(A)-prapynamido-beta-cyclodextrin and methyl propynoate, in aqueous solution, which gave only the cycloadducts from reaction of the cyclodextrin dipolarophile.

  DOI：

  10.1021/jo9817321

文献信息

• β-Cyclodextrin as a Scaffold for Supramolecular Chemistry, To Reverse the Regioselectivity of Nitrile Oxide Cycloadditions
  作者：Adam G. Meyer、Christopher J. Easton、Stephen F. Lincoln、Gregory W. Simpson

  DOI：10.1021/jo9817321

  日期：1998.11.1

  beta-Cyclodextrin has been used as a molecular scaffold, whereby tethering dipolarophiles to the cyclodextrin and then allowing preassociation of the modified cyclodextrins with aromatic nitrile oxides, as host-guest complexes, controls the relative orientations of the dipoles and the dipolarophiles in their cycloadditions. In this manner it has been possible to reverse the usual regioselectivity of cycloadditions of nitrile oxides, as illustrated by reactions with a terminal alkene, a terminal alkyne, and a 1,2-disubstituted alkene. For example, iii aqueous solution, 4-tert-butylbenzonitrile oxide reacted with 6(A)-deoxy-6(A)-propynamido-beta-cyclodextrin to give the corresponding 4- and 5-substituted isoxazoles, in a 15:1 ratio. With DMF as the solvent, to reduce the extent of host-guest complexation, the product ratio was 1:1.5. The role of complexation in these reactions is also demonstrated by contrasting these results with that of the reaction of the nitrile oxide with methyl propynoate, which afforded only the 5-substituted cycloaddition product. Molecular recognition by the cyclodextrin scaffolds was demonstrated through treatment of 4-tert-butylbenzonitrile oxide with an equimolar mixture of 6(A)-deoxy-6(A)-prapynamido-beta-cyclodextrin and methyl propynoate, in aqueous solution, which gave only the cycloadducts from reaction of the cyclodextrin dipolarophile.