1,6-anhydro-2-azido-3-O-(tert-butyldimethylsilyl)-2-deoxy-β-D-glucopyranose | 176213-92-6

• 分子结构分类: 有机化合物 - 有机杂环化合物 - 氧杂环己烷
• 英文名称: 1,6-anhydro-2-azido-3-O-(tert-butyldimethylsilyl)-2-deoxy-β-D-glucopyranose
• 英文别名: (1R,2R,3R,4R,5R)-4-azido-3-[tert-butyl(dimethyl)silyl]oxy-6,8-dioxabicyclo[3.2.1]octan-2-ol
• CAS: 176213-92-6
• 化学式: C₁₂H₂₃N₃O₄Si
• 分子量: 301.418
• InChiKey: CTOPNVBKGMGZEY-ISUQUUIWSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  2.17
• 重原子数：
  20
• 可旋转键数：
  4
• 环数：
  2.0
• sp3杂化的碳原子比例：
  1.0
• 拓扑面积：
  62.3
• 氢给体数：
  1
• 氢受体数：
  6

反应信息

• 作为反应物：
  描述：

  1,6-anhydro-2-azido-3-O-(tert-butyldimethylsilyl)-2-deoxy-β-D-glucopyranose 在 三氟化硼乙醚 、 silver perchlorate 、 乙酸肼 、 silver carbonate 、 三氟乙酸 作用下， 以 乙醇 、 二氯甲烷 、 N,N-二甲基甲酰胺 为溶剂， 生成 [(2R,3R,4R,5R)-5-azido-4-[tert-butyl(dimethyl)silyl]oxy-3-[(2S,3R,4S,5S,6R)-4,5-diacetyloxy-6-(acetyloxymethyl)-3-[(2R,3S,4R,5S,6S)-3,4,5-triacetyloxy-6-methylthian-2-yl]oxyoxan-2-yl]oxy-6-hydroxyoxan-2-yl]methyl acetate
  参考文献：
  名称：

  含5-硫-1-岩藻糖的血型抗原H 2型和Lewis X（Le x）的合成

  摘要：

  合成了两种血型抗原，分别是H型2和Lewis X三糖，它们含有5-硫基-1-岩藻糖而不是1-岩藻糖。使用2-叠氮基-2-脱氧乳糖衍生物11作为常见的二糖中间体。通过三氯乙亚氨酸酯方法对1，6-脱水-2-叠氮基-2-脱氧乳糖的衍生物的2'-OH和3-OH基团的5-硫-1-岩藻糖基化立体选择性地得到α-连接的三糖。

  DOI：

  10.1016/0040-4039(96)00124-4
• 作为产物：
  描述：

  1,6-anhydro-2-azido-2-deoxy-β-D-glucopyranose 在 咪唑 、 barium dihydroxide 、 四氯化钛 、 barium(II) oxide 作用下， 以 二氯甲烷 为溶剂， 反应 8.0h， 生成 1,6-anhydro-2-azido-3-O-(tert-butyldimethylsilyl)-2-deoxy-β-D-glucopyranose
  参考文献：
  名称：

  含5-硫-1-岩藻糖的血型抗原H 2型和Lewis X（Le x）的合成

  摘要：

  合成了两种血型抗原，分别是H型2和Lewis X三糖，它们含有5-硫基-1-岩藻糖而不是1-岩藻糖。使用2-叠氮基-2-脱氧乳糖衍生物11作为常见的二糖中间体。通过三氯乙亚氨酸酯方法对1，6-脱水-2-叠氮基-2-脱氧乳糖的衍生物的2'-OH和3-OH基团的5-硫-1-岩藻糖基化立体选择性地得到α-连接的三糖。

  DOI：

  10.1016/0040-4039(96)00124-4
• 作为试剂：
  描述：

  在 三氟甲磺酸三甲基硅酯 、 1,6-anhydro-2-azido-3-O-(tert-butyldimethylsilyl)-2-deoxy-β-D-glucopyranose 作用下， 以 乙腈 为溶剂， 以25%的产率得到[(2R,3S,4R,5R,6S)-6-acetamido-3,4-diacetyloxy-5-azidothian-2-yl]methyl acetate
  参考文献：
  名称：

  β-Selective Glycosidation of a 5-Thioglucosamine Derivative

  摘要：

  仲醇的第一个β-选择性化学5-硫代糖基化是用2-脱氧-2-邻苯二甲酰亚胺基-5-硫代葡萄糖衍生物实现的。基于各种官能团的结果，讨论了C2处的羰基官能团发挥嵌合辅助作用的要求。

  DOI：

  10.1246/cl.2008.1288

文献信息

• Synthesis of 5-Thio-<scp>l</scp>-fucose-Containing Disaccharides, as Sequence-Specific Inhibitors, and 2‘-Fucosyllactose, as a Substrate of α-<scp>l</scp>-Fucosidases
  作者：Masayuki Izumi、Osamu Tsuruta、Satoru Harayama、Hironobu Hashimoto

  DOI：10.1021/jo961725h

  日期：1997.2.1

  Four 5-thio-L-fucose-containing disaccharides having alpha(1-->6), alpha(1-->3), alpha(1-->4)GlcNAc, and alpha(1-->2-Gal linkages (compounds 1-4, respectively) were synthesized as potential alpha-L-fucosidase inhibitors. The glycosylation reactions using 2,3,4-tri-O-acetyl-5-thio-L-fucopyranosyl trichloroacetimidate as a glycosyl donor and BF3 . OEt(2) as a catalyst gave mainly alpha-linked disaccharides. Only alpha(1-->2)-linked disaccharide 4 showed inhibitory activity (K-i = 0.21 mM) against Bacillus alpha-L-fucosidase which hydrolyzes the Fuc alpha(1-->2) linkage specifically. The results suggested that sequence specificity of an enzyme could be estimated from the inhibitory activities of the compounds 1-4. In contrast, every disaccharide showed inhibitory activity (K-i = 30-91 mu M) against bovine epididymis alpha-L-fucosidase.
• A novel 5-thioglycosylation method with 1,5-dithioglycosyl donors: relevance to exo- versus endocyclic activation
  作者：Hideya Yuasa、Osamu Tsuruta、Hironobu Hashimoto

  DOI：10.1016/j.tetlet.2007.09.056

  日期：2007.11

  5-Thioglucosylation of a 1,6-anhydro-2-azido-2-deoxy-beta-D-glucopyranose derivative was carried out with various 1,5-dithioglucosyl donors. The use of per-O-acetyl donors resulted in poor yields of an alpha-disaccharide. On the other hand, per-O-benzyl donors selectively gave an alpha-disaccharide in good to excellent yields regardless of the anomeric configuration of the donors. To study the relevance of the glycosylation results to the pre-equilibrium of exo- versus endocyclic sulfide activation, the relative nucleophilicities of exo- and endocyclic sulfides were estimated from the regioselectivities in the electrophilic oxidation of the per-O-benzyl donors with m-chloroperbenzoic acid. The results obeyed stereoelectronic effects and the endocyclic sulfides were more nucleophilic than the exocyclic sulfides for both anomers of per-O-benzyl-1,5-dithioglucosyl donors, the relative nucleophilicities of the endocyclic over exocyclic sulfides being 67% and 100%, respectively, for the alpha- and beta-anomers. The results of the glycosidation and oxidation suggest that the glycosidation proceeded through an exocyclic cleavage mechanism despite the preferential endocyclic activation of 1,5-dithioglucosides. (c) 2007 Elsevier Ltd. All rights reserved.
• Synthesis of 5-thio-l-fucose-containing blood group antigens H-type 2 and Lewis X (Lex)
  作者：Masayuki Izumi、Osamu Tsuruta、Hironobu Hashimoto、Shin Yazawa

  DOI：10.1016/0040-4039(96)00124-4

  日期：1996.3

  Two blood group antigens, H-type 2 and Lewis X trisaccharides containing 5-thio-l-fucose instead of l-fucose, were synthesized. 2-Azido-2-deoxy-lactose derivative 11 was used as the common disaccharide intermediate. 5-Thio-l-fucosylation of the 2′-OH and 3-OH groups of 1,6-anhydro-2-azido-2-deoxy-lactose derivative by a trichloroacetimidate method gave α-linked trisaccharides stereoselectively.

  合成了两种血型抗原，分别是H型2和Lewis X三糖，它们含有5-硫基-1-岩藻糖而不是1-岩藻糖。使用2-叠氮基-2-脱氧乳糖衍生物11作为常见的二糖中间体。通过三氯乙亚氨酸酯方法对1，6-脱水-2-叠氮基-2-脱氧乳糖的衍生物的2'-OH和3-OH基团的5-硫-1-岩藻糖基化立体选择性地得到α-连接的三糖。
• β-Selective Glycosidation of a 5-Thioglucosamine Derivative
  作者：Hideya Yuasa、Osamu Tsuruta、Takuhiro Izumi、Terunao Takahara、Masayuki Izumi、Hironobu Hashimoto

  DOI：10.1246/cl.2008.1288

  日期：2008.12.5

  The first β-selective chemical 5-thioglycosylation of a secondary alcohol was attained with the 2-deoxy-2-phthalimido-5-thioglucose derivative. Requirements of the carbonyl functional groups at C2 to exert anchimeric assistance are discussed on the basis of the results with various functional groups.

  仲醇的第一个β-选择性化学5-硫代糖基化是用2-脱氧-2-邻苯二甲酰亚胺基-5-硫代葡萄糖衍生物实现的。基于各种官能团的结果，讨论了C2处的羰基官能团发挥嵌合辅助作用的要求。