3-C-azido-5-O-tert-butyldiphenylsilyl-1,2-O-isopropylidene-3-C-methoxycarbonyl-β-D-arabinofuranose | 352541-84-5

• 分子结构分类: 有机化合物 - 有机酸及其衍生物 - 羧酸及其衍生物
• 英文名称: 3-C-azido-5-O-tert-butyldiphenylsilyl-1,2-O-isopropylidene-3-C-methoxycarbonyl-β-D-arabinofuranose
• 英文别名: methyl (3aS,5S,6R,6aS)-6-azido-5-[[tert-butyl(diphenyl)silyl]oxymethyl]-2,2-dimethyl-5,6a-dihydro-3aH-furo[2,3-d][1,3]dioxole-6-carboxylate
• CAS: 352541-84-5
• 化学式: C₂₆H₃₃N₃O₆Si
• 分子量: 511.65
• InChiKey: NSTSVKQGXLMSEJ-ZUVQJFRASA-N

计算性质

• 辛醇/水分配系数(LogP)：
  3.66
• 重原子数：
  36
• 可旋转键数：
  9
• 环数：
  4.0
• sp3杂化的碳原子比例：
  0.5
• 拓扑面积：
  77.6
• 氢给体数：
  0
• 氢受体数：
  8

反应信息

• 作为反应物：
  描述：

  3-C-azido-5-O-tert-butyldiphenylsilyl-1,2-O-isopropylidene-3-C-methoxycarbonyl-β-D-arabinofuranose 在 palladium 10% on activated carbon 、 氢气 作用下， 以 四氢呋喃 、 甲醇 为溶剂， 20.0~60.0 ℃ 、101.33 kPa 条件下， 反应 17.5h， 生成 (5R,6S,8S,9S)-6-tert-butyldiphenylsilyloxymethyl-8,9-(dimethylmethylenedioxy)-3-phenyl-2-thioxo-7-oxa-1,3-diazaspiro[4.4]nonan-4-one
  参考文献：
  名称：

  Synthesis of conformationally-constrained thio(seleno)hydantoins and α-triazolyl lactones from d-arabinose as potential glycosidase inhibitors

  摘要：

  We have explored the rich structural diversity provided by an a-azido ester derived from D-arabinose as the source of sugar templates with reduced conformational flexibility. Using transient alpha-thioureido(selenoureido) esters we have prepared spiranic thio(seleno)hydantoins at the C-3 position of the sugar moiety. In this context, the first example of a stable spiranic alpha-lactam (or aziridinone) was isolated as a by-product in the hydrogenolysis of the starting alpha-azido ester. Furthermore, using copper(I)-catalyzed azido-alkyne cycloaddition (click chemistry), we have accessed bicyclic cis-fused alpha-triazolyl lactones fixed in the furanose form. Spiranic thiohydantoins turned out to be moderate, though selective, inhibitors of glycosidases, whereas their selenium isosters behaved as good free radical scavengers. (C) 2012 Elsevier Ltd. All rights reserved.

  DOI：

  10.1016/j.tet.2012.03.087
• 作为产物：
  描述：

  (3aS,5R,6R,6aS)-5-(((tert-butyldiphenylsilyl)oxy)methyl)-2,2-dimethyltetrahydrofuro[2,3-d][1,3]dioxol-6-ol 在 吡啶 、 chromium(VI) oxide 、 sodium azide 、 18-冠醚-6 、 乙酸酐 、 1,8-二氮杂双环[5.4.0]十一碳-7-烯 、 lithium hexamethyldisilazane 作用下， 以 四氢呋喃 、 二氯甲烷 为溶剂， 反应 4.5h， 生成 3-C-azido-5-O-tert-butyldiphenylsilyl-1,2-O-isopropylidene-3-C-methoxycarbonyl-β-D-arabinofuranose
  参考文献：
  名称：

  AZT的双环类似物的合成受异常O4'-内构象限制。

  摘要：

  [3.2.0]双环β-核苷类似物5已被设计为抗HIV药物AZT的构象受限类似物。因此描述了5及其α-端基异构体29的合成。由D-阿拉伯糖通过改良的Corey-Link程序完成立体合成，该程序立体选择性地合并了叠氮化物部分以及甲酯功能。当叔丁基二苯基甲硅烷基用作永久保护基时，氧杂环丁烷环的选择性形成失败。当使用对甲氧基苯基作为永久保护基时，通过酯的选择性还原，核碱基偶联，随后的端基异构体的分离和闭环程序有效地获得了5和29。核苷5在构型上受限于异常的O4'-内（东）构象，这是北方型和南方型构象之间的中间产物。然而，5和29均未显示出任何抗HIV活性。

  DOI：

  10.1021/jo010299j

文献信息

• Synthesis of conformationally-constrained thio(seleno)hydantoins and α-triazolyl lactones from d-arabinose as potential glycosidase inhibitors
  作者：Penélope Merino-Montiel、Óscar López、Eleuterio Álvarez、José G. Fernández-Bolaños

  DOI：10.1016/j.tet.2012.03.087

  日期：2012.6

  We have explored the rich structural diversity provided by an a-azido ester derived from D-arabinose as the source of sugar templates with reduced conformational flexibility. Using transient alpha-thioureido(selenoureido) esters we have prepared spiranic thio(seleno)hydantoins at the C-3 position of the sugar moiety. In this context, the first example of a stable spiranic alpha-lactam (or aziridinone) was isolated as a by-product in the hydrogenolysis of the starting alpha-azido ester. Furthermore, using copper(I)-catalyzed azido-alkyne cycloaddition (click chemistry), we have accessed bicyclic cis-fused alpha-triazolyl lactones fixed in the furanose form. Spiranic thiohydantoins turned out to be moderate, though selective, inhibitors of glycosidases, whereas their selenium isosters behaved as good free radical scavengers. (C) 2012 Elsevier Ltd. All rights reserved.
• Synthesis of a Bicyclic Analogue of AZT Restricted in an Unusual O4‘-<i>Endo</i> Conformation
  作者：Marianne H. Sørensen、Claus Nielsen、Poul Nielsen

  DOI：10.1021/jo010299j

  日期：2001.7.1

  beta-nucleoside analogue 5 has been designed as a conformationally restricted analogue of the anti-HIV drug AZT. The synthesis of 5 as well as its alpha-anomer 29 is hereby described. The synthesis was accomplished from D-arabinose via a modified Corey-Link procedure stereoselectively incorporating the azide moiety as well as a methyl ester function. When the tert-butyldiphenylsilyl group was used as a permanent

  [3.2.0]双环β-核苷类似物5已被设计为抗HIV药物AZT的构象受限类似物。因此描述了5及其α-端基异构体29的合成。由D-阿拉伯糖通过改良的Corey-Link程序完成立体合成，该程序立体选择性地合并了叠氮化物部分以及甲酯功能。当叔丁基二苯基甲硅烷基用作永久保护基时，氧杂环丁烷环的选择性形成失败。当使用对甲氧基苯基作为永久保护基时，通过酯的选择性还原，核碱基偶联，随后的端基异构体的分离和闭环程序有效地获得了5和29。核苷5在构型上受限于异常的O4'-内（东）构象，这是北方型和南方型构象之间的中间产物。然而，5和29均未显示出任何抗HIV活性。