3-deoxy-2,5,6-tri-O-benzoyl-L-gulono-γ-lactone | 145369-05-7

• 分子结构分类: 有机化合物 - 有机酸及其衍生物 - 羧酸及其衍生物
• 英文名称: 3-deoxy-2,5,6-tri-O-benzoyl-L-gulono-γ-lactone
• 英文别名: 3-deoxy-2,5,6-tri-O-benzoylgulonic γ-lactone；[(2S)-2-benzoyloxy-2-[(2S,4S)-4-benzoyloxy-5-oxooxolan-2-yl]ethyl] benzoate
• CAS: 145369-05-7
• 化学式: C₂₇H₂₂O₈
• 分子量: 474.467
• InChiKey: YPCFWFWOBPJZJV-VABKMULXSA-N

物化性质

• 沸点：
  600.6±44.0 °C(predicted)
• 密度：
  1.35±0.1 g/cm3(Temp: 20 °C; Press: 760 Torr)(predicted)

计算性质

• 辛醇/水分配系数(LogP)：
  5.1
• 重原子数：
  35
• 可旋转键数：
  11
• 环数：
  4.0
• sp3杂化的碳原子比例：
  0.19
• 拓扑面积：
  105
• 氢给体数：
  0
• 氢受体数：
  8

反应信息

• 作为反应物：
  描述：

  (-)-薄荷酮 、 3-deoxy-2,5,6-tri-O-benzoyl-L-gulono-γ-lactone 在 六甲基磷酰三胺 、 samarium diiodide 作用下， 以 四氢呋喃 为溶剂， 以53%的产率得到5,6-di-O-benzoyl-3-deoxy-L-gulono-γ-lactone and menthone adduct
  参考文献：
  名称：

  Branched-chain carbohydrate lactones from a samarium(II) iodide-promoted serial deoxygenation-carbonyl addition reaction

  摘要：

  A new deoxygenation-carbonyl addition reaction mediated by samarium(II) iodide (SmI2) in THF/HMPA was examined with carbohydrate lactones and several substrates containing an alpha-alkoxy carboxylic ester. In a single reaction, these compounds were deoxygenated and subsequently coupled to several ketones by a carbonyl addition reaction. The first reactions studied simple ester and ketone adducts which were later elaborated to more complex optically active carbohydrate lactones appended to terpene ketones. Simple esters smoothly afforded beta-hydroxy carbonyl products. Fully benzoate-protected 3-deoxycarbohydrate lactones were reacted with simple ketones to produce C2-branched sugars. The attendant carbonyl addition to the least sterically hindered face of the aldonolactone provided the major products. Moderate diastereoselectivities (up to 5:1) were observed in the simple ketone products as determined by difference NOE studies. Finally, the terpene ketones, (-)-menthone or (+)-dihydrocarvone, were coupled to 3-deoxycarbohydrate lactones which gave C2-branched sugars with very high diastereoselectivities (up to 99:1).

  DOI：

  10.1021/jo00067a045
• 作为产物：
  描述：

  L-古洛糖酸-gamma-内酯 在 palladium on activated charcoal 吡啶 、 氢气 、 三乙胺 作用下， 以 氯仿 、 乙酸乙酯 为溶剂， 25.0 ℃ 、101.33 kPa 条件下， 反应 5.0h， 生成 3-deoxy-2,5,6-tri-O-benzoyl-L-gulono-γ-lactone
  参考文献：
  名称：

  Branched-chain carbohydrate lactones from a samarium(II) iodide-promoted serial deoxygenation-carbonyl addition reaction

  摘要：

  A new deoxygenation-carbonyl addition reaction mediated by samarium(II) iodide (SmI2) in THF/HMPA was examined with carbohydrate lactones and several substrates containing an alpha-alkoxy carboxylic ester. In a single reaction, these compounds were deoxygenated and subsequently coupled to several ketones by a carbonyl addition reaction. The first reactions studied simple ester and ketone adducts which were later elaborated to more complex optically active carbohydrate lactones appended to terpene ketones. Simple esters smoothly afforded beta-hydroxy carbonyl products. Fully benzoate-protected 3-deoxycarbohydrate lactones were reacted with simple ketones to produce C2-branched sugars. The attendant carbonyl addition to the least sterically hindered face of the aldonolactone provided the major products. Moderate diastereoselectivities (up to 5:1) were observed in the simple ketone products as determined by difference NOE studies. Finally, the terpene ketones, (-)-menthone or (+)-dihydrocarvone, were coupled to 3-deoxycarbohydrate lactones which gave C2-branched sugars with very high diastereoselectivities (up to 99:1).

  DOI：

  10.1021/jo00067a045

文献信息

• Highly stereoselective couplings of carbohydrate lactones with terpene ketones promoted by SmI2
  作者：Eric J. Enholm、Shujun Jiang

  DOI：10.1016/s0040-4039(00)60008-4

  日期：1992.10

  Lactone 3-deoxycarbohydrates were reacted with samarium diiodide (SmI2) in THF/HMPA and the terpene ketones, (−)-menthone or (+)-dihydrocarvone; a serial reductive deoxygenation and an attendant carbonyl addition reaction afforded C2 branched sugars with high diastereoselectivities (up to 99:1).

  使内酯3-脱氧碳水化合物与二碘化sa（SmI 2）在THF / HMPA中和萜烯酮（-）-薄荷酮或（+）-二氢香芹酮反应; 连续的还原性脱氧和伴随的羰基加成反应得到具有高非对映选择性（高达99∶1）的C 2支链糖。
• Enholm, Eric J.; Jiang, Shujun, Heterocycles, 1992, vol. 34, # 12, p. 2247 - 2252
  作者：Enholm, Eric J.、Jiang, Shujun

  DOI：——

  日期：——
• Branched-chain carbohydrate lactones from a samarium(II) iodide-promoted serial deoxygenation-carbonyl addition reaction
  作者：Eric J. Enholm、Shujun Jiang、Khalil Abboud

  DOI：10.1021/jo00067a045

  日期：1993.7

  A new deoxygenation-carbonyl addition reaction mediated by samarium(II) iodide (SmI2) in THF/HMPA was examined with carbohydrate lactones and several substrates containing an alpha-alkoxy carboxylic ester. In a single reaction, these compounds were deoxygenated and subsequently coupled to several ketones by a carbonyl addition reaction. The first reactions studied simple ester and ketone adducts which were later elaborated to more complex optically active carbohydrate lactones appended to terpene ketones. Simple esters smoothly afforded beta-hydroxy carbonyl products. Fully benzoate-protected 3-deoxycarbohydrate lactones were reacted with simple ketones to produce C2-branched sugars. The attendant carbonyl addition to the least sterically hindered face of the aldonolactone provided the major products. Moderate diastereoselectivities (up to 5:1) were observed in the simple ketone products as determined by difference NOE studies. Finally, the terpene ketones, (-)-menthone or (+)-dihydrocarvone, were coupled to 3-deoxycarbohydrate lactones which gave C2-branched sugars with very high diastereoselectivities (up to 99:1).