(+)-(1R,4R,5R,6S,7R)-7-endo,4-exo-diacetoxy-6-endo-<(2',3',4',6'-tetra-O-acetyl-α-D-glucopyranosyl)methyl>-2,8-dioxabicyclo<3.2.1>octan-3-one | 134160-58-0

• 分子结构分类: 有机化合物 - 脂质和类脂质分子 - 脂肪酰基
• 英文名称: (+)-(1R,4R,5R,6S,7R)-7-endo,4-exo-diacetoxy-6-endo-<(2',3',4',6'-tetra-O-acetyl-α-D-glucopyranosyl)methyl>-2,8-dioxabicyclo<3.2.1>octan-3-one
• 英文别名: (+)-(1R,4R,5R,6S,7R)-7-endo,4-exo-diacetoxy-6-endo-[(2',3',4',6'-tetra-O-acetyl-α-D-glucopyranosyl)methyl]-2,8-dioxabicyclo[3.2.1]octan-3-one
• CAS: 134160-58-0
• 化学式: C₂₅H₃₂O₁₆
• 分子量: 588.519
• InChiKey: FSGVEYAUBXYVNB-CQIPCORVSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  -0.74
• 重原子数：
  41.0
• 可旋转键数：
  9.0
• 环数：
  3.0
• sp3杂化的碳原子比例：
  0.72
• 拓扑面积：
  202.56
• 氢给体数：
  0.0
• 氢受体数：
  16.0

反应信息

• 作为反应物：
  描述：

  (+)-(1R,4R,5R,6S,7R)-7-endo,4-exo-diacetoxy-6-endo-<(2',3',4',6'-tetra-O-acetyl-α-D-glucopyranosyl)methyl>-2,8-dioxabicyclo<3.2.1>octan-3-one 在 4-二甲氨基吡啶 吡啶 、 lithium aluminium tetrahydride 、 氯化亚砜 作用下， 以 四氢呋喃 为溶剂， 反应 35.5h， 生成 (+)-methyl 3-deoxy-3-<(2',3',4',6'-tetra-O-acetyl-α-D-glucopyranosyl)methyl>-2,4,6-tri-O-acetyl-β-L-manno-hexopyranoside
  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：

  (+)-(1S,3R,4R,5S,6R)-6-endo,3-exo-diacetoxy-5-endo-<(2',3',4',6'-tetra-O-acetyl-α-D-glucopyranosyl)methyl>-7-oxabicyclo<2.2.1>heptan-2-one 在 碳酸氢钠 、 间氯过氧苯甲酸 作用下， 以 二氯甲烷 为溶剂， 反应 0.33h， 以94%的产率得到(+)-(1R,4R,5R,6S,7R)-7-endo,4-exo-diacetoxy-6-endo-<(2',3',4',6'-tetra-O-acetyl-α-D-glucopyranosyl)methyl>-2,8-dioxabicyclo<3.2.1>octan-3-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

• Synthesis of α-(1→3)- and α-(1→4)-linked c-disaccharides using (+)-7-oxabicyclo[2.2.1]hept-5-en-2-one (“naked sugar”).
  作者：R. Mampuya Bimwala、Pierre Vogel

  DOI：10.1016/0040-4039(91)80349-b

  日期：1991.3