(-)-(1R,4R,5R,6S)-6-endo-{[(tert-butyl)dimethylsilyl]oxy}-5-exo-methoxy-7-oxabicyclo[2.2.1]heptan-2-one | 352426-51-8

• 分子结构分类: 有机化合物 - 有机杂环化合物 - 二氢呋喃
• 英文名称: (-)-(1R,4R,5R,6S)-6-endo-{[(tert-butyl)dimethylsilyl]oxy}-5-exo-methoxy-7-oxabicyclo[2.2.1]heptan-2-one
• 英文别名: (1R,4R,5R,6S)-6-[tert-butyl(dimethyl)silyl]oxy-5-methoxy-7-oxabicyclo[2.2.1]heptan-2-one
• CAS: 352426-51-8
• 化学式: C₁₃H₂₄O₄Si
• 分子量: 272.417
• InChiKey: ZQASWXFLAKLTJV-WRWGMCAJSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  2.13
• 重原子数：
  18
• 可旋转键数：
  4
• 环数：
  2.0
• sp3杂化的碳原子比例：
  0.92
• 拓扑面积：
  44.8
• 氢给体数：
  0
• 氢受体数：
  4

反应信息

• 作为反应物：
  描述：

  氰甲基磷酸二乙酯 、 (-)-(1R,4R,5R,6S)-6-endo-{[(tert-butyl)dimethylsilyl]oxy}-5-exo-methoxy-7-oxabicyclo[2.2.1]heptan-2-one 在 potassium hydride 作用下， 以 四氢呋喃 为溶剂， 反应 0.42h， 以65%的产率得到(-)-(2E)-{(1S,4R,5R,6R)-6-endo-{[(tert-butyl)dimethylsilyl]oxy}-5-exo-methoxy-7-oxabicyclo[2.2.1]hept-2-yliden}acetonitrile
  参考文献：
  名称：

  Total Synthesis of (−)-Bauhinin

  摘要：

  The total synthesis of the naturally occurring cyanoglucoside (-)-bauhinin (1) was achieved starting from the optically pure oxatrinorbornenone 2 in 12 steps and 8% overall yield. The aglycone of (-)-bauhinin was easily obtained from the optically pure oxatrinorbornenone derivative 6 by a Wittig-Horner reaction followed by the opening of the oxa bridge. Glycosidation with tetra-O-isobutyryl-D-glucosyl bromide 9 as the reagent in the Koenigs-Knorr reaction afforded glucoside 10 in 58% yield, which, after photoisomerization and deprotection, gave (-)-bauhinin (1).

  DOI：

  10.1002/1522-2675(20010418)84:4<890::aid-hlca890>3.0.co;2-q
• 作为产物：
  描述：

  (-)-(1R,4R,5R,6S)-6-endo-(benzyloxy)-5-exo-hydroxy-7-oxabicyclo<2.2.1>heptan-2-one 在 palladium on activated charcoal 咪唑 、 氢气 、 silver(l) oxide 作用下， 以 乙酸乙酯 、 N,N-二甲基甲酰胺 、 乙腈 为溶剂， 反应 20.0h， 生成 (-)-(1R,4R,5R,6S)-6-endo-{[(tert-butyl)dimethylsilyl]oxy}-5-exo-methoxy-7-oxabicyclo[2.2.1]heptan-2-one
  参考文献：
  名称：

  Total Synthesis of (−)-Bauhinin

  摘要：

  The total synthesis of the naturally occurring cyanoglucoside (-)-bauhinin (1) was achieved starting from the optically pure oxatrinorbornenone 2 in 12 steps and 8% overall yield. The aglycone of (-)-bauhinin was easily obtained from the optically pure oxatrinorbornenone derivative 6 by a Wittig-Horner reaction followed by the opening of the oxa bridge. Glycosidation with tetra-O-isobutyryl-D-glucosyl bromide 9 as the reagent in the Koenigs-Knorr reaction afforded glucoside 10 in 58% yield, which, after photoisomerization and deprotection, gave (-)-bauhinin (1).

  DOI：

  10.1002/1522-2675(20010418)84:4<890::aid-hlca890>3.0.co;2-q

文献信息

• Total Synthesis of (−)-Bauhinin
  作者：Delphine Josien-Lefebvre、Guillaume Desmares、Claude Le Drian

  DOI：10.1002/1522-2675(20010418)84:4<890::aid-hlca890>3.0.co;2-q

  日期：2001.4.18

  The total synthesis of the naturally occurring cyanoglucoside (-)-bauhinin (1) was achieved starting from the optically pure oxatrinorbornenone 2 in 12 steps and 8% overall yield. The aglycone of (-)-bauhinin was easily obtained from the optically pure oxatrinorbornenone derivative 6 by a Wittig-Horner reaction followed by the opening of the oxa bridge. Glycosidation with tetra-O-isobutyryl-D-glucosyl bromide 9 as the reagent in the Koenigs-Knorr reaction afforded glucoside 10 in 58% yield, which, after photoisomerization and deprotection, gave (-)-bauhinin (1).