2-bromo-3,4,6-tris-O-(tert-butyldimethylsilyl)-2-deoxy-α-D-mannopyranose | 192129-71-8

• 分子结构分类: 有机化合物 - 有机氧化合物
• 英文名称: 2-bromo-3,4,6-tris-O-(tert-butyldimethylsilyl)-2-deoxy-α-D-mannopyranose
• 英文别名: TBDMS(-3)[TBDMS(-4)][TBDMS(-6)]a-Man2Br；(2S,3S,4S,5R,6R)-3-bromo-4,5-bis[[tert-butyl(dimethyl)silyl]oxy]-6-[[tert-butyl(dimethyl)silyl]oxymethyl]oxan-2-ol
• CAS: 192129-71-8
• 化学式: C₂₄H₅₃BrO₅Si₃
• 分子量: 585.842
• InChiKey: LTNWXYLBNHEXAM-XNTOXWQXSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  7.27
• 重原子数：
  33
• 可旋转键数：
  10
• 环数：
  1.0
• sp3杂化的碳原子比例：
  1.0
• 拓扑面积：
  57.2
• 氢给体数：
  1
• 氢受体数：
  5

反应信息

• 作为反应物：
  描述：

  2-bromo-3,4,6-tris-O-(tert-butyldimethylsilyl)-2-deoxy-α-D-mannopyranose 在 caesium carbonate 作用下， 以 甲醇 为溶剂， 反应 24.0h， 生成 2,5-anhydro-3,4,6-tris-O-(tert-butyldimethylsilyl)-aldehydo-D-mannose 、 2,5-anhydro-3,4,6-tris-O-(tert-butyldimethylsilyl)-aldehydo-D-glucose
  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
• 作为产物：
  描述：

  D-葡萄烯糖 在 咪唑 、 N-溴代丁二酰亚胺(NBS) 、 碳酸氢钠 作用下， 以 四氢呋喃 、 水 、 N,N-二甲基甲酰胺 为溶剂， 反应 22.0h， 生成 2-bromo-3,4,6-tris-O-(tert-butyldimethylsilyl)-2-deoxy-α-D-mannopyranose
  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