methyl 3-O-acetyl-4,6-O-benzylidene-2-O-diazoacetyl-α-D-mannopyranoside | 1353896-04-4

• 分子结构分类: 有机化合物 - 有机杂环化合物 - 吡喃二恶英
• 英文名称: methyl 3-O-acetyl-4,6-O-benzylidene-2-O-diazoacetyl-α-D-mannopyranoside
• 英文别名: methyl 4,6-O-benzylidene-2-O-diazoacetyl-3-O-acetyl-α-D-mannopyranoside；[(2R,4aR,6S,7S,8S,8aR)-8-acetyloxy-6-methoxy-2-phenyl-4,4a,6,7,8,8a-hexahydropyrano[3,2-d][1,3]dioxin-7-yl] 2-diazoacetate
• CAS: 1353896-04-4
• 化学式: C₁₈H₂₀N₂O₈
• 分子量: 392.365
• InChiKey: JTAKCYDPKLGSLZ-YYOXGBMASA-N

计算性质

• 辛醇/水分配系数(LogP)：
  1.3
• 重原子数：
  28
• 可旋转键数：
  7
• 环数：
  3.0
• sp3杂化的碳原子比例：
  0.5
• 拓扑面积：
  91.5
• 氢给体数：
  0
• 氢受体数：
  9

反应信息

• 作为反应物：
  描述：

  methyl 3-O-acetyl-4,6-O-benzylidene-2-O-diazoacetyl-α-D-mannopyranoside 在 dirhodium tetraacetate 作用下， 以 1,2-二氯乙烷 为溶剂， 以90%的产率得到(2R,4aR,5aS,8aS,9S,9aR)-5a-methoxy-7-oxo-2-phenyloctahydrofuro[2',3':5,6]pyrano[3,2-d][1,3]dioxin-9-yl acetate
  参考文献：
  名称：

  Gram-Scale Quaternarization of the Anomeric Position of Carbohydrates: Dramatic Effects of Molecular Sieves on Rhodium(II)-Mediated Decomposi­tion of Diazo Sugars

  摘要：

  The optimization of rhodium(II) carbene mediated quaternarization of the anomeric position of carbohydrates is reported. Preparation of ketopyranosides in good and reliable yields requires reverse addition of the substrate to a highly diluted suspension of the catalyst in refluxing 1,2-dichloroethane, as well as addition of a carefully controlled amount of molecular sieves, and vigorous stirring. Following these optimized reaction conditions, functionalization of the anomeric position of carbohydrates can finally be performed on a preparative scale.

  DOI：

  10.1055/s-0032-1317013
• 作为产物：
  描述：

  在 N,N′-双(对甲苯磺酰)肼 、 1,8-二氮杂双环[5.4.0]十一碳-7-烯 作用下， 以 四氢呋喃 为溶剂， 生成 methyl 3-O-acetyl-4,6-O-benzylidene-2-O-diazoacetyl-α-D-mannopyranoside
  参考文献：
  名称：

  Rh(II) Carbene-Mediated Synthesis of Methyl α- and β-Ketopyranosides: Preparation of Carbene Precursors, Quaternarization of the Anomeric Position, and Ring Opening of γ-Lactones

  摘要：

  Methyl alpha- and beta-ketopyranosides were efficiently prepared by carbene-mediated quaternarization of the anomeric position of corresponding aldopyranosides. Preparation of carbene precursors proved to be tedious and required a two-step procedure involving first bromoacetylation, followed by diazo-transfer with N,N'-ditosylhydrazine and DBU. Selective functionalization of the anomeric C-H bond was then achieved under Rh-2(OAc)(4) or Rh-2(acam)(4) catalysis. Finally, ring opening of the resulting gamma-lactones delivered alpha- and beta-ketopyranosides with the anomeric position functionalized by an independent chain.

  DOI：

  10.1080/07328303.2011.614983