3,4,6-tri-O-benzyl-2-deoxy-β-D-arabinohexopyranosyl hydroperoxide | 861100-42-7

• 分子结构分类: 有机化合物 - 有机氧化合物
• 英文名称: 3,4,6-tri-O-benzyl-2-deoxy-β-D-arabinohexopyranosyl hydroperoxide
• 英文别名: 3,4,6-tri-O-benzyl-2-deoxy-β-D-glucosyl hydroperoxide；2,4,6-tri-O-benzyl-β-D-arabino-hexopyranosyl hydroperoxide；(2R,3S,4R,6S)-6-hydroperoxy-3,4-bis(phenylmethoxy)-2-(phenylmethoxymethyl)oxane
• CAS: 861100-42-7
• 化学式: C₂₇H₃₀O₆
• 分子量: 450.532
• InChiKey: ZRDHGVAUKIGUHJ-XDZXDJIYSA-N

物化性质

• 沸点：
  605.1±55.0 °C(Predicted)
• 密度：
  1.22±0.1 g/cm3(Predicted)

计算性质

• 辛醇/水分配系数(LogP)：
  4
• 重原子数：
  33
• 可旋转键数：
  11
• 环数：
  4.0
• sp3杂化的碳原子比例：
  0.33
• 拓扑面积：
  66.4
• 氢给体数：
  1
• 氢受体数：
  6

反应信息

• 作为反应物：
  描述：

  3,4,6-tri-O-benzyl-2-deoxy-β-D-arabinohexopyranosyl hydroperoxide 、 methyl 3,4,6-tri-O-benzyl-2-deoxy-D-galactopyranoside 在 (+)-10-camphorsulfonic acid 作用下， 以 二氯甲烷 为溶剂， 生成 3,4,6-tri-O-benzyl-2-deoxy-β-D-glucopyranosyl(3,4,6-tri-O-benzyl-2-deoxy-α-D-galactopyranosyl)peroxide
  参考文献：
  名称：

  Bisglycosyl Peroxides

  摘要：

  三O-苄基-d-甘露糖在per-O-苄基-2-脱氧-α-或per-O-苄基-2-脱氧-β-d-糖苷过氧化物的处理下，生成相应的双糖苷过氧化物。在所有情况下，形成了新的α-糖苷键。过氧化物的形成不是一个可逆的过程；在所施加的反应条件下，我们没有观察到β,α-过氧化物转变为相应的α,α-化合物。

  DOI：

  10.1055/s-2007-991090
• 作为产物：
  描述：

  3,4,6-tri-O-benzyl-β-D-arabino-hexopyranosyl (1-methoxy-1-methyl)ethyl peroxide 在 硫酸 作用下， 以 丙酮 为溶剂， 生成 3,4,6-tri-O-benzyl-2-deoxy-β-D-arabinohexopyranosyl hydroperoxide
  参考文献：
  名称：

  Glycosyl hydroperoxides derived from 2-deoxysugars

  摘要：

  Oxidation of 3,4,6-tri-O-benzyl-2-deoxy-D-glucose and D-galactose or their t-butyl glycosides to the corresponding glycosyl hydroperoxides can be performed with hydrogen peroxide in the presence of an acid catalyst. Several reaction conditions and their influence on the effectiveness of the oxidation are discussed. Separation of the alpha - and beta-anomers of the glycosyl hydroperoxides was achieved through mixed peroxide formation by reaction of the hydroperoxide group with 2-methoxypropene and subsequent deprotection. (C) 2010 Elsevier Ltd. All rights reserved.

  DOI：

  10.1016/j.carres.2010.09.005
• 作为试剂：
  描述：

  苯亚甲基苯乙酮 在 3,4,6-tri-O-benzyl-2-deoxy-β-D-arabinohexopyranosyl hydroperoxide 、 sodium hydroxide 作用下， 以 水 、 甲苯 为溶剂， 生成 (2S,3R)-2,3-epoxy-1,3-diphenylpropan-1-one 、 (2R,3S)-epoxy-1,3-diphenylpropan-1-one
  参考文献：
  名称：

  通过使用糖基氢过氧化物对亲电烯烃进行对映选择性环氧化。

  摘要：

  衍生自3,4,6-三-O-苄基-半乳糖和葡萄糖的端基氢过氧化物用于萘醌（12），查尔酮（13），（E）-1,2-二苯甲酰基乙烯（14）和（ E）-异丁酰基-苯基乙烯（15）。在氢氧化钠存在下，环氧化显示出异常的高不对称诱导。通过钾离子交换钠导致低的不对称诱导。这些结果指出了抗衡离子的关键作用，并强烈建议在环氧化过程的过渡态中，氢过氧化物和烯烃这两种试剂均会发生碱性离子的配位。DFT B3LYP / 6-31G *水平上反应机理的理论研究与实验结果非常吻合。

  DOI：

  10.1002/chem.200800051

文献信息

• New stable anomeric hydroperoxides derived from 2-deoxysugars; enantioselective epoxidation of 2-methyl-1,4-naphthoquinone
  作者：Wioletta Kośnik、Andrew V. Stachulski、Marek Chmielewski

  DOI：10.1016/j.tetasy.2005.04.009

  日期：2005.6

  3.5-Di- or 3,4,6-tri-O-substituted-2-deoxysugars or their glycosides can be oxidized with hydrogen peroxide in the presence of an acid catalyst to the corresponding anomeric hydroperoxides, which are relatively stable, can be separated into pure anomers by column chromatography and stored in a refrigerator without visible decomposition. The hydroperoxides thus obtained were used for the enantioselective epoxidation of 2-methyl-1,4-naphthoquinone with ees in the range 28-47%. (c) 2005 Elsevier Ltd. All rights reserved.
• Enantioselective Epoxidation of Electrophilic Olefins by Using Glycosyl Hydroperoxides
  作者：Wioletta Kośnik、Wojciech Bocian、Lech Kozerski、Igor Tvaroška、Marek Chmielewski

  DOI：10.1002/chem.200800051

  日期：2008.7.7

  Anomeric hydroperoxides derived from 3,4,6-tri-O-benzyl-galactose and glucose were used for enantioselective epoxidation of naphthoquinone (12), chalcone (13), (E)-1,2-dibenzoyl ethylene (14) and (E)-iso-butyryl-phenyl ethylene (15). In the presence of sodium hydroxide, the epoxidations showed exceptional high asymmetric induction. The exchange of sodium by a potassium ion resulted in a low asymmetric

  衍生自3,4,6-三-O-苄基-半乳糖和葡萄糖的端基氢过氧化物用于萘醌（12），查尔酮（13），（E）-1,2-二苯甲酰基乙烯（14）和（ E）-异丁酰基-苯基乙烯（15）。在氢氧化钠存在下，环氧化显示出异常的高不对称诱导。通过钾离子交换钠导致低的不对称诱导。这些结果指出了抗衡离子的关键作用，并强烈建议在环氧化过程的过渡态中，氢过氧化物和烯烃这两种试剂均会发生碱性离子的配位。DFT B3LYP / 6-31G *水平上反应机理的理论研究与实验结果非常吻合。
• Bisglycosyl Peroxides
  作者：Marek Chmielewski、Wioletta Kośnik、Barbara Grzeszczyk

  DOI：10.1055/s-2007-991090

  日期：——

  Tri-O-benzyl-d-glycal treated with per-O-benzyl-2-deoxy-α- or per-O-benzyl-2-deoxy-β-d-glycosyl hydroperoxide affords the corresponding bisglycosyl peroxides. In all cases a new α-glycosidic bond is formed. Formation of the peroxide is not a reversible process; under applied reaction conditions, we did not observe rearrangement of β,α-peroxide into the corresponding α,α-compounds.

  三O-苄基-d-甘露糖在per-O-苄基-2-脱氧-α-或per-O-苄基-2-脱氧-β-d-糖苷过氧化物的处理下，生成相应的双糖苷过氧化物。在所有情况下，形成了新的α-糖苷键。过氧化物的形成不是一个可逆的过程；在所施加的反应条件下，我们没有观察到β,α-过氧化物转变为相应的α,α-化合物。
• Glycosyl hydroperoxides derived from 2-deoxysugars
  作者：Barbara Szechner、Zofia Urbańczyk-Lipkowska、Marek Chmielewski

  DOI：10.1016/j.carres.2010.09.005

  日期：2010.11

  Oxidation of 3,4,6-tri-O-benzyl-2-deoxy-D-glucose and D-galactose or their t-butyl glycosides to the corresponding glycosyl hydroperoxides can be performed with hydrogen peroxide in the presence of an acid catalyst. Several reaction conditions and their influence on the effectiveness of the oxidation are discussed. Separation of the alpha - and beta-anomers of the glycosyl hydroperoxides was achieved through mixed peroxide formation by reaction of the hydroperoxide group with 2-methoxypropene and subsequent deprotection. (C) 2010 Elsevier Ltd. All rights reserved.