1,1²-anhydro-4,6-O-benzylidene-3-O-tert-butyldimethylsilyl-2-deoxy-1-(2-hydroxymethylphenyl)-α-D-arabino-hexopyranose | 139903-09-6

• 分子结构分类: 有机化合物 - 有机杂环化合物
• 英文名称: 1,1²-anhydro-4,6-O-benzylidene-3-O-tert-butyldimethylsilyl-2-deoxy-1-(2-hydroxymethylphenyl)-α-D-arabino-hexopyranose
• CAS: 139903-09-6
• 化学式: C₂₆H₃₄O₅Si
• 分子量: 454.638
• InChiKey: FIVDQVAZNOHCTA-HROMDODWSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  5.66
• 重原子数：
  32.0
• 可旋转键数：
  3.0
• 环数：
  5.0
• sp3杂化的碳原子比例：
  0.54
• 拓扑面积：
  46.15
• 氢给体数：
  0.0
• 氢受体数：
  5.0

反应信息

• 作为产物：
  描述：

  1,5-anhydro-4,6-O-benzylidene-3-O-tert-butyldimethylsilyl-2-deoxy-1-tributylstannyl-D-arabino-hex-1-enitol 在 四(三苯基膦)钯 2-溴苄醇 、 sodium carbonate 作用下， 以 甲苯 为溶剂， 反应 24.0h， 以73%的产率得到1,1²-anhydro-4,6-O-benzylidene-3-O-tert-butyldimethylsilyl-2-deoxy-1-(2-hydroxymethylphenyl)-α-D-arabino-hexopyranose
  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