(3S,4S,5R,6R)-4,5-Bis-(tert-butyl-dimethyl-silanyloxy)-6-(tert-butyl-dimethyl-silanyloxymethyl)-3-iodo-tetrahydro-pyran-2-one | 192129-77-4

• 分子结构分类: 有机化合物 - 有机杂环化合物 - 内酯类
• 英文名称: (3S,4S,5R,6R)-4,5-Bis-(tert-butyl-dimethyl-silanyloxy)-6-(tert-butyl-dimethyl-silanyloxymethyl)-3-iodo-tetrahydro-pyran-2-one
• CAS: 192129-77-4
• 化学式: C₂₄H₅₁IO₅Si₃
• 分子量: 630.827
• InChiKey: ASEUKDUQOLNNIJ-IYWMVGAKSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  7.52
• 重原子数：
  33.0
• 可旋转键数：
  7.0
• 环数：
  1.0
• sp3杂化的碳原子比例：
  0.96
• 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：

  sodium methylate 、 (3S,4S,5R,6R)-4,5-Bis-(tert-butyl-dimethyl-silanyloxy)-6-(tert-butyl-dimethyl-silanyloxymethyl)-3-iodo-tetrahydro-pyran-2-one 以 甲醇 为溶剂， 反应 1.0h， 以83%的产率得到methyl 2,5-anhydro-3,4,6-tris-O-tert-butyldimethylsilyl-D-gluconate
  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：

  3,4,6-tris-O-(tert-butyldimethylsilyl)-2-deoxy-2-iodo-α-D-mannopyranose 在 tetrapropylammonium perruthenate 、 4 A molecular sieve 、 N-甲基吗啉氧化物 作用下， 以 二氯甲烷 为溶剂， 反应 2.5h， 以95%的产率得到(3S,4S,5R,6R)-4,5-Bis-(tert-butyl-dimethyl-silanyloxy)-6-(tert-butyl-dimethyl-silanyloxymethyl)-3-iodo-tetrahydro-pyran-2-one
  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