(2R,4aR,6S,6aS,11aS,11bR)-6-methoxy-2,10-diphenyloctahydro-8H-[1,3]dioxino[4',5':5,6]pyrano[3,4-b][1,4]dioxepin-8-one | 1256137-88-8

• 分子结构分类: 有机化合物 - 有机杂环化合物 - 二恶烷
• 英文名称: (2R,4aR,6S,6aS,11aS,11bR)-6-methoxy-2,10-diphenyloctahydro-8H-[1,3]dioxino[4',5':5,6]pyrano[3,4-b][1,4]dioxepin-8-one
• CAS: 1256137-88-8
• 化学式: C₂₃H₂₄O₇
• 分子量: 412.439
• InChiKey: ACSPDOAJVYFSCG-TUKNXGSWSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  2.91
• 重原子数：
  30.0
• 可旋转键数：
  3.0
• 环数：
  5.0
• sp3杂化的碳原子比例：
  0.43
• 拓扑面积：
  72.45
• 氢给体数：
  0.0
• 氢受体数：
  7.0

反应信息

• 作为产物：
  描述：

  methyl 3-O-benzyl-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20%的产率得到(2R,4aR,5aS,8aS,9S,9aR)-9-(benzyloxy)-5a-methoxy-2-phenylhexahydrofuro[2′,3′:5,6]pyrano[3,2-d][1,3]dioxin-7-(8aH)-one
  参考文献：
  名称：

  Rh(II) Carbene-Promoted Activation of the Anomeric C−H Bond of Carbohydrates: A Stereospecific Entry toward α- and β-Ketopyranosides

  摘要：

  In this communication we report a new strategy toward ketopyranosides based on a carbene-mediated activation of the anomeric C-H bond of carbohydrates. By forming a new carbon-carbon bond after a glycosylation step, this approach enables the preparation of both alpha- and beta-ketopyranosides from advanced precursors.

  DOI：

  10.1021/ja1054065

文献信息

• 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.