(1R,3R,4R,4aR,9aR)-1-Benzyloxy-4-bromo-3-hydroxy-6,6,8,8-tetraisopropyl-tetrahydro-2,5,7,9-tetraoxa-6,8-disila-benzocycloheptene-3-carboxylic acid methyl ester | 188003-33-0

• 分子结构分类: 有机化合物 - 有机杂环化合物 - 吡喃
• 英文名称: (1R,3R,4R,4aR,9aR)-1-Benzyloxy-4-bromo-3-hydroxy-6,6,8,8-tetraisopropyl-tetrahydro-2,5,7,9-tetraoxa-6,8-disila-benzocycloheptene-3-carboxylic acid methyl ester
• 英文别名: methyl (5aR,6R,8R,9R,9aR)-9-bromo-8-hydroxy-6-phenylmethoxy-2,2,4,4-tetra(propan-2-yl)-5a,6,9,9a-tetrahydropyrano[3,4-f][1,3,5,2,4]trioxadisilepine-8-carboxylate
• CAS: 188003-33-0
• 化学式: C₂₆H₄₃BrO₈Si₂
• 分子量: 619.698
• InChiKey: IKOPFLUVHCUJTD-YLLXKFEGSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  5.51
• 重原子数：
  37
• 可旋转键数：
  9
• 环数：
  3.0
• sp3杂化的碳原子比例：
  0.73
• 拓扑面积：
  92.7
• 氢给体数：
  1
• 氢受体数：
  8

反应信息

• 作为反应物：
  描述：

  (1R,3R,4R,4aR,9aR)-1-Benzyloxy-4-bromo-3-hydroxy-6,6,8,8-tetraisopropyl-tetrahydro-2,5,7,9-tetraoxa-6,8-disila-benzocycloheptene-3-carboxylic acid methyl ester 在 silver(l) oxide 作用下， 以 四氢呋喃 、 N,N-二甲基甲酰胺 为溶剂， 反应 15.0h， 以92%的产率得到(1aS,3R,3aR,8aS,8bS)-3-Benzyloxy-5,5,7,7-tetraisopropyl-tetrahydro-1,2,4,6,8-pentaoxa-5,7-disila-cyclopropa[3,4]benzo[1,2]cycloheptene-1a-carboxylic acid methyl ester
  参考文献：
  名称：

  Regio- and Stereoselective Synthesis of β-d-Gluco-, α-l-Ido-, and α-l-Altropyranosiduronic Acids from Δ⁴-Uronates

  摘要：

  The stereoselective synthesis of beta-D-glucopyranosiduronic, alpha-L-idopyranosiduronic, and alpha-L-altropyranosiduronic acids has been performed from different Delta(4)-uronate monosaccharides. Bromination of the C-4,5 double bond provided the trans-diaxial bromohydrin derivatives, which were converted to the corresponding epoxides in high yields. Direct reduction of the epoxides using boranetetrahydrofuran complex led to the corresponding glucuronic acids in low to good yields. Glucuronic acids were also obtained in satisfactory yields through a two-steps procedure involving bromination of the epoxide with titanium(IV) bromide followed by reduction using tributyltin hydride. Lewis acid-catalyzed rearrangement of these epoxides led to the corresponding alpha-L C-4 ketopyranosides adopting the C-1(4) chair conformation. Hydride reduction afforded the alpha-L-idopyranosiduronic or the alpha-L-altropyranosiduronic acids, the stereoselectivity of the reduction being controlled by the appropriate substitution pattern.

  DOI：

  10.1021/jo981477k
• 作为产物：
  描述：

  苄基beta-D-吡喃葡糖苷酸甲酯三乙酸酯 在 N-溴代丁二酰亚胺(NBS) 、 水 、 sodium methylate 、 1,8-二氮杂双环[5.4.0]十一碳-7-烯 作用下， 以 四氢呋喃 、 吡啶 、 甲醇 、 二氯甲烷 为溶剂， 反应 12.0h， 生成 (1R,3R,4R,4aR,9aR)-1-Benzyloxy-4-bromo-3-hydroxy-6,6,8,8-tetraisopropyl-tetrahydro-2,5,7,9-tetraoxa-6,8-disila-benzocycloheptene-3-carboxylic acid methyl ester
  参考文献：
  名称：

  Regio and stereoselective conversion of Δ4-uronic acids to l-Ido- and d-glucopyranosiduronic acids

  摘要：

  Synthesis of L-ido- and D-glucopyranosiduronic acids was performed starting from protected Delta(4)-uronic acids 3a-f. Bromination of the C-4,5 double bond provided the trans-diaxial bromohydrin derivatives 6a-d, which were converted to the corresponding epoxides 7a-d in high yields. Direct reduction of these epoxides using borane-tetrahydrofuran complex afforded the o-glucopyranosiduronic acids 9b-d, while Lewis acid rearrangment through the C-4 keto intermediate 10b-d afforded the L-idopyranosiduronic acids 11b-d. (C) 1997, Elsevier Science Ltd.

  DOI：

  10.1016/s0040-4039(96)02514-2