1,2²-anhydro-4,6-O-benzylidene-1-(4,6-dibenzyloxy-2-hydroxymethylphenyl)-α-D-glucopyranose | 139903-10-9

• 分子结构分类: 有机化合物
• 英文名称: 1,2²-anhydro-4,6-O-benzylidene-1-(4,6-dibenzyloxy-2-hydroxymethylphenyl)-α-D-glucopyranose
• 英文别名: (2'R,3S,4'aR,7'R,8'R,8'aS)-2'-phenyl-4,6-bis(phenylmethoxy)spiro[1H-2-benzofuran-3,6'-4a,7,8,8a-tetrahydro-4H-pyrano[3,2-d][1,3]dioxine]-7',8'-diol
• CAS: 139903-10-9
• 化学式: C₃₄H₃₂O₈
• 分子量: 568.623
• InChiKey: XNWFDMUHWIDXIT-DFWAUOKRSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  3.7
• 重原子数：
  42
• 可旋转键数：
  7
• 环数：
  7.0
• sp3杂化的碳原子比例：
  0.29
• 拓扑面积：
  95.8
• 氢给体数：
  2
• 氢受体数：
  8

反应信息

• 作为反应物：
  描述：

  1,2²-anhydro-4,6-O-benzylidene-1-(4,6-dibenzyloxy-2-hydroxymethylphenyl)-α-D-glucopyranose 在 palladium on activated charcoal 氢气 作用下， 以 甲醇 、 乙酸乙酯 为溶剂， 生成 1,1'-anhydro-1-C-[2',4'-dihydroxy-6'-(hydroxymethyl)-phenyl]-α-D-glucopyranose
  参考文献：
  名称：

  Papulacandins and chaetiacandin: a stereoselective route to their basic skeleton by a palladium-mediated arylation of 4,6-O-benzylidene-3-O-tert-butyldimethylsilyl-1-tributylstannyl-d-glucal

  摘要：

  Palladium(0)-catalysed coupling of 1,5-anhydro-4,6-O-benzylidene-3-O-tert-butyldimethylsilyl-2-deoxy-1-tributylstannyl-D-arabino-hex-1-enitol (7) with 3,5-dibenzyloxy-2-bromobenzyl alcohol gave 1,1(2)-anhydro-4,6-O-benzylidene-3-O-tert-butyldimethylsilyl-2-deoxy-1-(4,6-dibenzyloxy-2-hydroxymethyl-phenyl-alpha-D-arabino-hexopyranose (13). The same reaction buffered by sodium carbonate provided 1,5-anhydro-4,6-O-benzylidene-3-O-tert-butyldimethylsilyl-2-deoxy-1-(4,6-dibenzyloxy-2-hydroxymethyl-phenyl)-D-arabino-hex-1-enitol (11). Stereoselective oxidative spiroacetalisation of 11 provided 1,(2)-anhydro-4,6-O-benzylidene-3-O-tert-butyldimethylsilyl-1-(4,6-dibenzyloxy-2-hydroxymethyl-phenyl)-alpha-D-glucopyranose (15), the basic tricyclic structure of papulacandins. In a model study, 15 was converted in three steps into 1,1(2)-anhydro-1-(4,6-dihydroxy-2-hydroxymethylphenyl)-3-O-octadecanoyl-alpha-D-glucopyranose (24), a structural analogue of papulacandin D. Moreover, stereoselective hydroboration-oxidation of 11 furnished 2-(4,6-O-benzylidene-3-O-tert-butyldimethylsilyl-beta-D-glucopyranosyl)-3,5-dibenzyloxy-1-hydroxymethylbenzene (26), the structural skeleton of the chaetiacandin 3.

  DOI：

  10.1016/0008-6215(92)80014-r
• 作为产物：
  描述：

  1,1²-anhydro-4,6-O-benzylidene-3-O-tert-butyldimethylsilyl-1-(4,6-dibenzyloxy-2-hydroxymethylphenyl)-α-D-glucopyranose 在 四丁基氯化铵 作用下， 以 四氢呋喃 为溶剂， 反应 4.0h， 以85%的产率得到1,2²-anhydro-4,6-O-benzylidene-1-(4,6-dibenzyloxy-2-hydroxymethylphenyl)-α-D-glucopyranose
  参考文献：
  名称：

  Papulacandins and chaetiacandin: a stereoselective route to their basic skeleton by a palladium-mediated arylation of 4,6-O-benzylidene-3-O-tert-butyldimethylsilyl-1-tributylstannyl-d-glucal

  摘要：

  Palladium(0)-catalysed coupling of 1,5-anhydro-4,6-O-benzylidene-3-O-tert-butyldimethylsilyl-2-deoxy-1-tributylstannyl-D-arabino-hex-1-enitol (7) with 3,5-dibenzyloxy-2-bromobenzyl alcohol gave 1,1(2)-anhydro-4,6-O-benzylidene-3-O-tert-butyldimethylsilyl-2-deoxy-1-(4,6-dibenzyloxy-2-hydroxymethyl-phenyl-alpha-D-arabino-hexopyranose (13). The same reaction buffered by sodium carbonate provided 1,5-anhydro-4,6-O-benzylidene-3-O-tert-butyldimethylsilyl-2-deoxy-1-(4,6-dibenzyloxy-2-hydroxymethyl-phenyl)-D-arabino-hex-1-enitol (11). Stereoselective oxidative spiroacetalisation of 11 provided 1,(2)-anhydro-4,6-O-benzylidene-3-O-tert-butyldimethylsilyl-1-(4,6-dibenzyloxy-2-hydroxymethyl-phenyl)-alpha-D-glucopyranose (15), the basic tricyclic structure of papulacandins. In a model study, 15 was converted in three steps into 1,1(2)-anhydro-1-(4,6-dihydroxy-2-hydroxymethylphenyl)-3-O-octadecanoyl-alpha-D-glucopyranose (24), a structural analogue of papulacandin D. Moreover, stereoselective hydroboration-oxidation of 11 furnished 2-(4,6-O-benzylidene-3-O-tert-butyldimethylsilyl-beta-D-glucopyranosyl)-3,5-dibenzyloxy-1-hydroxymethylbenzene (26), the structural skeleton of the chaetiacandin 3.

  DOI：

  10.1016/0008-6215(92)80014-r