2,5-anhydro-3,4,6-tri-O-benzyl-D-talose | 37699-02-8

• 分子结构分类: 有机化合物 - 有机氧化合物
• 英文名称: 2,5-anhydro-3,4,6-tri-O-benzyl-D-talose
• 英文别名: (3S,4R,5R)-3,4-bis(benzyloxy)-5-((benzyloxy)methyl)tetrahydrofuran-2-carbaldehyde；2,5-anhydro-3,4,6-tris-O-(phenylmethyl)--D-mannose；2,5-anhydro-3,4,6-tri-O-benzyl-aldehydo-D-altrohexofuranose
• CAS: 37699-02-8；94273-27-5；94283-95-1；122194-15-4
• 化学式: C₂₇H₂₈O₅
• 分子量: 432.516
• InChiKey: FHNGZJPNWWCNKW-BCQPQQEMSA-N

物化性质

• 沸点：
  571.7±50.0 °C(Predicted)
• 密度：
  1.19±0.1 g/cm3(Predicted)

计算性质

• 辛醇/水分配系数(LogP)：
  4.34
• 重原子数：
  32.0
• 可旋转键数：
  11.0
• 环数：
  4.0
• sp3杂化的碳原子比例：
  0.3
• 拓扑面积：
  53.99
• 氢给体数：
  0.0
• 氢受体数：
  5.0

反应信息

• 作为反应物：
  描述：

  2,5-anhydro-3,4,6-tri-O-benzyl-D-talose 在 palladium on activated charcoal sodium tetrahydroborate 、 高氯酸 、 偶氮二异丁腈 、 硫酸 、 氢气 、 三正丁基氢锡 、 N,N'-硫羰基二咪唑 、 三苯基膦 、 偶氮二甲酸二乙酯 作用下， 以 1,4-二氧六环 、 吡啶 、 甲醇 为溶剂， 生成 2,5-anhydro-4,6-di-O-benzoyl-1-(N-3-benzoylthymin-1-yl)-3-deoxy-D-ribo-hexitol
  参考文献：
  名称：

  Synthesis of Homo-C-D4T and Homo-C-Thymidine

  摘要：

  beta-C-Vinyl glycoside of D-arabinofuranose was converted to the beta-C-hydroxymethyl glycoside 12 which was condensed with N-3-benzoyl thymine under Mitsunobu conditions to furnish homo-C-analog 14 of the 2',3'-dideoxy-2',3'-didehydrothymidine (D4T). Synthesis of the homo-C-thymidine 18 was accomplished by the same procedure from compound 15.

  DOI：

  10.1080/07328319708006130
• 作为产物：
  描述：

  methyl 3,4,6-tri-O-benzyl-2-O-(trifluoromethanesulfonyl)-β-D-glucopyranoside 以 吡啶 、 水 、 N,N-二甲基甲酰胺 为溶剂， 反应 0.08h， 以100%的产率得到2,5-anhydro-3,4,6-tri-O-benzyl-D-talose
  参考文献：
  名称：

  Chemistry of glucal halohydrins(II): An unusual protecting group effect in the competitive formation of formyl furanosides and methyl glycosides

  摘要：

  A remarkable protecting group influence was observed in the base-induced reaction of protected halohydrins derived from D-glycals. Tri-O-methyl and tri-O-benzyl halohydrins react with cesium carbonate in methanol at room temperature to give methyl glycosides as the major product and unsaturated formyl furanosides as the minor product. Whereas, the tri-O-tert-butyldimethylsilyl (t-BuMe2Si)-protected halohydrins reacted with cesium carbonate in methanol at room temperature to give a mixture of epimeric formyl furanosides, and at reflux to give an unsaturated formyl furanoside, as the only products. The tri-O-methyl and tri-O-benzyl halohydrins react slowly at elevated temperature to give predominantly furans. In comparison, the tri-O-t-BuMe2Si halohydrins reacted completely after five minutes to give a mixture of epimeric formyl furanosides. The tri-O-t-BuMe2Si iodohydrins were oxidized to the corresponding iodolactones, which also underwent a based-induced ring contraction in methanol to give the furanose 1-methylcarboxylate esters. (C) 1997 Elsevier Science Ltd.

  DOI：

  10.1016/s0008-6215(97)00054-2

文献信息

• Rearrangements in the Course of Fluorination by Diethylaminosulfur Trifluoride at C-2 of Glycopyranosides: Some New Parameters
  作者：Karl Dax、Martin Albert、David Hammond、Carina Illaszewicz、Thomas Purkarthofer、Martin Tscherner、Hansjörg Weber

  DOI：10.1007/s007060200019

  日期：2002.4.1

  -decalin types those with an additional 1,2- trans -configuration are prone to 1,2-aglycon migration and, again, entry of the fluoride at C-1. Additional pathways like alkoxy group migration, substitution under retention of configuration, or orthoester formation, are possible by participation of a suitably located neighbouring group at C-3 inasmuch as an alkoxy group interferes from an antiperiplanar orientation

  通过19 F NMR光谱监测 了一系列在O-2处未保护并具有各种构型的21种糖苷与 DAST （二乙基氨基三氟化硫）的反应。借助于由此获得的每种产品的变音数据集（位移值和耦合常数），可以确定操作机制。通过将这些发现与离析物结构的立体化学细节相关联，可以推导控制反应路径选择的新参数。该评估得出的结果是，与所有其他可能性相比，强烈赞成在环氧的C-2进攻后环收缩和氟在C-1进入。例外是manno系列的所有派生类以及 反式- 十氢萘型结构，在4,6-O-亚苄基乙缩醛形成后存在，离析基的环取代基在C-4和C-5处于二位（ 反式 ）方向。根据这些， d 通常，具有额外的1，2- 反式构型的反式 -甘露聚糖苷和 反式- 十氢化萘的类型 倾向于1，2-糖苷配基迁移，并且氟化物再次进入C-1。诸如烷氧基迁移，构型保留下的取代或原酸酯形成等其他途径也可能通过位于C-3处适当定位的邻近基团的参与而实现，因为烷氧
• Asymmetric cyclopropanation of allylic ethers: cleavage and regeneration of the chiral auxiliary
  作者：Andre B. Charette、Bernard Cote

  DOI：10.1021/jo00056a028

  日期：1993.2

  The ring contraction reaction of 2-O-(trifluoromethyl)sulfonyl]oxy]-beta-D-glucopyranosides and their corresponding a-anomers is reported. The rearrangement was shown to occur under extremely mild basic conditions to allow isolation of acid-sensitive optically active substituted cyclopropylmethanols. The chiral auxiliary can be regenerated by converting the C-glucofuranoside, byproduct of the rearrangement, into tri-O-benzyl-D-glucal (two steps).
• Carbohydrates as chiral auxiliaries: asymmetric cyclopropanation reaction of acyclic olefins
  作者：Andre B. Charette、Bernard Cote、Jean Francois Marcoux

  DOI：10.1021/ja00021a052

  日期：1991.10