(+)-(1R,4R,5R,6R)-3-methylidene-5-exo,6-exo-(isopropylidenedioxy)-7-oxabicyclo<2.2.1>heptan-2-one | 139426-55-4

• 分子结构分类: 有机化合物 - 有机氧化合物
• 英文名称: (+)-(1R,4R,5R,6R)-3-methylidene-5-exo,6-exo-(isopropylidenedioxy)-7-oxabicyclo<2.2.1>heptan-2-one
• 英文别名: (+)-(1R,4R,5R,6R)-3-methylidene-5-exo,6-exo-(isopropylidenedioxy)-7-oxabicyclo[2.2.1]heptan-2-one；(1R,2R,6R,7R)-4,4-dimethyl-9-methylidene-3,5,10-trioxatricyclo[5.2.1.02,6]decan-8-one
• CAS: 139426-55-4
• 化学式: C₁₀H₁₂O₄
• 分子量: 196.203
• InChiKey: KFGMDSWWNWQYID-XAVMHZPKSA-N

物化性质

• 沸点：
  306.1±42.0 °C(Predicted)
• 密度：
  1.29±0.1 g/cm3(Predicted)

计算性质

• 辛醇/水分配系数(LogP)：
  0.3
• 重原子数：
  14
• 可旋转键数：
  0
• 环数：
  3.0
• sp3杂化的碳原子比例：
  0.7
• 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：

  (+)-(1R,4R,5R,6R)-3-methylidene-5-exo,6-exo-(isopropylidenedioxy)-7-oxabicyclo<2.2.1>heptan-2-one 、 2,3,4,6-四乙酰氧基-alpha-D-吡喃葡萄糖溴化物 在 2-(2-cyanopropan-2-yldiazenyl)-2-methylpropanenitrile 、 三正丁基氢锡 作用下， 以 甲苯 为溶剂， 以68%的产率得到(1R,3R,4R,5R,6R)-3-endo-<(2',3',4',6'-tetra-O-acetyl-α,β-D-gluco-pyranosyl)methyl>-5-exo,6-exo-(isopropylidenedioxy)-7-oxabicyclo<2.2.1>heptan-2-one
  参考文献：
  名称：

  Enantiomerically pure 7-oxabicyclo[2.2.1]hept-5-en-2-yl derivatives (naked sugars) as synthetic intermediates. 18. Synthesis of .alpha.-(1.fwdarw.2)-, .alpha.-(1.fwdarw.3)-, .alpha.-(1.fwdarw.4)-, and .alpha.-(1.fwdarw.5)-C-linked disaccharides through 2,3,4,6-tetra-O-acetylglucopyranosyl radical additions to 3-methylidene-7-oxabicyclo[2.2.1]heptan-2-one derivatives

  摘要：

  The ''naked sugar'' (+)-1 (1R,2S,4R)-2-cyano-7-oxabicyclo[2.2.1]hept-5-en-2-yl (1S')-camphanate) has been converted into (+)-(1R,4R,5R,6R)-3-methylidene-5-exo,6-exo(isopropylidenedioxy)-7-oxabicyclo[2.2.1]heptan-2-one ((+)-3) and (-)-(1S,4R,5R,6R)-5-exo-(benzeneselenyl)-6-endo-chloro-3-methylidene-7-oxabicyclo[2.2.1]heptan-2-one ((-)-26). Reductive addition of 2,3,4,6-tetra-O-acetylglucopyranosyl radical onto (+)-3 and (-)-26 were highly stereoselective giving exclusively 3-endo-(glucosylmethyl)-7-oxabicyclo[2.2.1]heptan-2-one derivatives. The anomeric selectivity (alpha-C-glucoside vs beta-C-glucoside) was 5.5:1 with (+)-3 and 8:1 with (-)-26. The C-glucosides so-obtained were transformed into alpha-(1 --> 2)-, alpha-(1 --> 3)-, alpha-(1 --> 4)-, and alpha-(1 --> 5)-C-linked disaccharide derivatives which combine alpha-D-glucopyranose with L-altro-hexonolactone, L-manno-hexonolactone, L-mannose, and L-(talo-hexofuranosid)uronic acid, respectively.

  DOI：

  10.1021/jo00033a032
• 作为产物：
  描述：

  n,n-二甲基亚甲基碘化胺 、 (-)-2-<<(tert-butyl)dimethylsilyl>oxy>-5,6-exo-(isopropylidenedioxy)-7-oxabicyclo<2.2.1>hept-2-ene 在 六甲基磷酰三胺 作用下， 以 四氢呋喃 为溶剂， 反应 1.5h， 以53%的产率得到(+)-(1R,4R,5R,6R)-3-methylidene-5-exo,6-exo-(isopropylidenedioxy)-7-oxabicyclo<2.2.1>heptan-2-one
  参考文献：
  名称：

  Enantiomerically pure 7-oxabicyclo[2.2.1]hept-5-en-2-yl derivatives (naked sugars) as synthetic intermediates. 18. Synthesis of .alpha.-(1.fwdarw.2)-, .alpha.-(1.fwdarw.3)-, .alpha.-(1.fwdarw.4)-, and .alpha.-(1.fwdarw.5)-C-linked disaccharides through 2,3,4,6-tetra-O-acetylglucopyranosyl radical additions to 3-methylidene-7-oxabicyclo[2.2.1]heptan-2-one derivatives

  摘要：

  The ''naked sugar'' (+)-1 (1R,2S,4R)-2-cyano-7-oxabicyclo[2.2.1]hept-5-en-2-yl (1S')-camphanate) has been converted into (+)-(1R,4R,5R,6R)-3-methylidene-5-exo,6-exo(isopropylidenedioxy)-7-oxabicyclo[2.2.1]heptan-2-one ((+)-3) and (-)-(1S,4R,5R,6R)-5-exo-(benzeneselenyl)-6-endo-chloro-3-methylidene-7-oxabicyclo[2.2.1]heptan-2-one ((-)-26). Reductive addition of 2,3,4,6-tetra-O-acetylglucopyranosyl radical onto (+)-3 and (-)-26 were highly stereoselective giving exclusively 3-endo-(glucosylmethyl)-7-oxabicyclo[2.2.1]heptan-2-one derivatives. The anomeric selectivity (alpha-C-glucoside vs beta-C-glucoside) was 5.5:1 with (+)-3 and 8:1 with (-)-26. The C-glucosides so-obtained were transformed into alpha-(1 --> 2)-, alpha-(1 --> 3)-, alpha-(1 --> 4)-, and alpha-(1 --> 5)-C-linked disaccharide derivatives which combine alpha-D-glucopyranose with L-altro-hexonolactone, L-manno-hexonolactone, L-mannose, and L-(talo-hexofuranosid)uronic acid, respectively.

  DOI：

  10.1021/jo00033a032

文献信息

• Enantiomerically pure 7-oxabicyclo[2.2.1]hept-5-en-2-yl derivatives (naked sugars) as synthetic intermediates. 18. Synthesis of .alpha.-(1.fwdarw.2)-, .alpha.-(1.fwdarw.3)-, .alpha.-(1.fwdarw.4)-, and .alpha.-(1.fwdarw.5)-C-linked disaccharides through 2,3,4,6-tetra-O-acetylglucopyranosyl radical additions to 3-methylidene-7-oxabicyclo[2.2.1]heptan-2-one derivatives
  作者：R. Mampuya Bimwala、Pierre Vogel

  DOI：10.1021/jo00033a032

  日期：1992.3

  The ''naked sugar'' (+)-1 (1R,2S,4R)-2-cyano-7-oxabicyclo[2.2.1]hept-5-en-2-yl (1S')-camphanate) has been converted into (+)-(1R,4R,5R,6R)-3-methylidene-5-exo,6-exo(isopropylidenedioxy)-7-oxabicyclo[2.2.1]heptan-2-one ((+)-3) and (-)-(1S,4R,5R,6R)-5-exo-(benzeneselenyl)-6-endo-chloro-3-methylidene-7-oxabicyclo[2.2.1]heptan-2-one ((-)-26). Reductive addition of 2,3,4,6-tetra-O-acetylglucopyranosyl radical onto (+)-3 and (-)-26 were highly stereoselective giving exclusively 3-endo-(glucosylmethyl)-7-oxabicyclo[2.2.1]heptan-2-one derivatives. The anomeric selectivity (alpha-C-glucoside vs beta-C-glucoside) was 5.5:1 with (+)-3 and 8:1 with (-)-26. The C-glucosides so-obtained were transformed into alpha-(1 --> 2)-, alpha-(1 --> 3)-, alpha-(1 --> 4)-, and alpha-(1 --> 5)-C-linked disaccharide derivatives which combine alpha-D-glucopyranose with L-altro-hexonolactone, L-manno-hexonolactone, L-mannose, and L-(talo-hexofuranosid)uronic acid, respectively.