[(2R,4aR,6S,7S,8R,8aR)-7-hydroxy-6-methoxy-6-[2-[methoxy(methyl)amino]-2-oxoethyl]-2-phenyl-4a,7,8,8a-tetrahydro-4H-pyrano[3,2-d][1,3]dioxin-8-yl] 2,2-dimethylpropanoate | 1256138-46-1

• 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: [(2R,4aR,6S,7S,8R,8aR)-7-hydroxy-6-methoxy-6-[2-[methoxy(methyl)amino]-2-oxoethyl]-2-phenyl-4a,7,8,8a-tetrahydro-4H-pyrano[3,2-d][1,3]dioxin-8-yl] 2,2-dimethylpropanoate
• CAS: 1256138-46-1
• 化学式: C₂₃H₃₃NO₉
• 分子量: 467.516
• InChiKey: AOEIKUFVQKGCHZ-WCYDREAOSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  1.1
• 重原子数：
  33
• 可旋转键数：
  8
• 环数：
  3.0
• sp3杂化的碳原子比例：
  0.65
• 拓扑面积：
  113
• 氢给体数：
  1
• 氢受体数：
  9

反应信息

• 作为产物：
  描述：

  methyl 4,6-O-benzylidene-2-O-diazoacetyl-3-O-pivaloyl-α-D-mannopyranoside 在 dirhodium tetraacetate 、 三甲基铝 作用下， 以 二氯甲烷 、 1,2-二氯乙烷 、 甲苯 为溶剂， 反应 1.83h， 生成 [(2R,4aR,6S,7S,8R,8aR)-7-hydroxy-6-methoxy-6-[2-[methoxy(methyl)amino]-2-oxoethyl]-2-phenyl-4a,7,8,8a-tetrahydro-4H-pyrano[3,2-d][1,3]dioxin-8-yl] 2,2-dimethylpropanoate
  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

文献信息

• Carbene-Mediated Functionalization of the Anomeric CH Bond of Carbohydrates: Scope and Limitations
  作者：Mélissa Boultadakis-Arapinis、Elise Prost、Vincent Gandon、Pascale Lemoine、Serge Turcaud、Laurent Micouin、Thomas Lecourt

  DOI：10.1002/chem.201203725

  日期：2013.5.3

  Herein we investigate the scope and limitations of a new synthetic approach towards α‐ and β‐ketopyranosides relying on the functionalization of the anomeric CH bond of carbohydrates by insertion of a metal carbene. A key bromoacetate grafted at the 2‐position is the cornerstone of a stereoselective glycosylation/diazotransfer/quaternarization sequence that makes possible the construction of a quaternary

  在此，我们对调查α-，β-ketopyranosides依靠异头C的官能一种新的合成方法的范围和局限性通过插入金属卡宾来实现碳水化合物的H键。在2位接枝的关键溴乙酸盐是立体选择性糖基化/重氮转移/季铵化序列的基石，这使得在完全控制立体化学的情况下构建季中心成为可能。该序列显示出对碳水化合物化学中常用的保护基的良好耐受性，并以良好的效率产生了季二糖。在具有更受限构象的二糖的情况下，该功能化过程可能会受到目标异头异构体位置旁边的空间需求的阻碍。另外，在糖基化步骤期间形成瞬时原酸酯也可能降低合成序列的整体效率。
• 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
  作者：Mélissa Boultadakis-Arapinis、Camille Lescot、Laurent Micouin、Thomas Lecourt

  DOI：10.1080/07328303.2011.614983

  日期：2011.9.1

  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.