2,3,4,6-Tetra-O-benzyl-1-O-β-D-glucopyranose | 82561-63-5

• 分子结构分类: 有机化合物 - 有机氧化合物
• 英文名称: 2,3,4,6-Tetra-O-benzyl-1-O-β-D-glucopyranose
• 英文别名: Bn(-2)[Bn(-3)][Bn(-4)][Bn(-6)]Glc(b)-O-pivaloyl；[(2S,3R,4S,5R,6R)-3,4,5-tris(phenylmethoxy)-6-(phenylmethoxymethyl)oxan-2-yl] 2,2-dimethylpropanoate
• CAS: 82561-63-5
• 化学式: C₃₉H₄₄O₇
• 分子量: 624.774
• InChiKey: WLSYQWSQLMDDLN-MANRWTMFSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  7
• 重原子数：
  46
• 可旋转键数：
  16
• 环数：
  5.0
• sp3杂化的碳原子比例：
  0.36
• 拓扑面积：
  72.4
• 氢给体数：
  0
• 氢受体数：
  7

反应信息

• 作为反应物：
  描述：

  2,3,4,6-Tetra-O-benzyl-1-O-β-D-glucopyranose 在 palladium on activated charcoal 氢气 作用下， 以 乙醇 、 乙酸乙酯 为溶剂， 反应 5.0h， 生成 β-D-glucopyranosyl 1-pivaloate
  参考文献：
  名称：

  Stereoselective synthesis of 1-O-pivaloyl .beta.-D-glucopyranuronic acid

  摘要：

  DOI：

  10.1021/jo00020a044
• 作为产物：
  描述：

  2,3,4,6-四苄基-D-吡喃葡萄糖 在 吡啶 、 碘代三甲硅烷 、 四丁基硫酸氢铵 、 sodium hexamethyldisilazane 作用下， 以 二氯甲烷 为溶剂， 反应 4.83h， 生成 2,3,4,6-Tetra-O-benzyl-1-O-β-D-glucopyranose
  参考文献：
  名称：

  Anionic Additions to Glycosyl Iodides:  Highly Stereoselective Syntheses of β C-, N-, and O-Glycosides¹

  摘要：

  Classically, glycosyl halides are activated as glycosyl donors by metal chelation under Koenigs-Knorr or Helferich conditions. These reactions often proceed through oxonium formation, and the stereochemical outcome is dictated by the anomeric effect and/or the nature of the protecting group on the C2 hydroxyl. Alternatively, glycosyl halides may undergo direct displacement of the halide by an incoming nucleophile in an S(N)2 mechanism. The latter reaction is far less common, and before this study it was primarily performed with glycosyl bromides. Having recently shown that both alpha and beta glycosyl iodides could be efficiently generated, we embarked upon an investigation of nucleophilic additions to glycosyl iodides. The studies reported herein show that additions of stabilized anions to alpha-glycosyl iodides proceed with inversion of stereochemistry to give beta-glycosides, even in the absence of a C2 participatory group. Glucosyl, galactosyl, and mannosyl iodides were studied, and the combined results indicate that the reactivity of 2,3,4,6-tetra-O-benzyl-alpha-D-galactosyl iodide > 2,3,4,6-tetra-O-benzyl-alpha-D-glucosyl iodide > 2,3,4,6-tetra-O-benzyl-alpha-D-mannosyl iodide. Both the glucosyl and galactosyl iodides are susceptible to E-2 elimination when treated with highly basic anions. In contrast, the mannosyl iodide undergoes substitution to give the 1,2 cis configuration. The overall sequence involves reaction of an anomeric acetate with trimethylsilyl iodide with in vacuo removal of the resulting trimethylsilyl acetate. The iodide is then treated with a nucleophile without further characterization. A variety of nucleophiles were stereoselectively added to the glycosyl halides providing beta-, C-, N-, and O-glycosides.

  DOI：

  10.1021/jo970922t

文献信息

• Syntheses of 1-O-acylaldose derivatives via the corresponding O-glycosylpseudoureas
  作者：Hideo Tsutsumi、Yoshiharu Ishido

  DOI：10.1016/0008-6215(82)85008-8

  日期：1982.12

  Abstract A series of 1- O -acylaldose derivatives was prepared in good yield through the reaction of 1,3-dialkyl- O -glycosylpseudoureas with carboxylic acids.

  摘要通过1，3-二烷基-O-糖基假单胞菌与羧酸的反应，高收率地制备了一系列1-O-酰基醛糖衍生物。
• STEREOSELECTIVE SYNTHESIS OF 1-<i>O</i>-ACYL-D-GLUCOPYRANOSE FROM 1-HYDROXY SUGAR AND ACYL FLUORIDES BY THE PROMOTION OF CESIUM FLUORIDE
  作者：Shin-ichiro Shoda、Teruaki Mukaiyama

  DOI：10.1246/cl.1982.861

  日期：1982.6.5

  In the presence of cesium fluoride, the reaction of 2,3,4,6-tetra-O-benzyl-d-glucopyranose with acyl fluorides affords the corresponding glucosyl esters in good yields under essentially neutral condition. The α⁄β ratio of produced glucosyl esters is greatly affected by reaction conditions and predominant formations of each anomer is achieved by procedures described herein.

  在氟化铯存在下，2,3,4,6-四-O-苄基-d-吡喃葡萄糖与酰氟反应在基本中性条件下以良好的产率提供相应的葡萄糖酯。所产生的葡萄糖酯的α/β比率很大程度上受反应条件影响，并且每种端基异构体的主要形成是通过本文描述的程序实现的。
• Bols, Mikael; Hansen, Henrik Claus; Smith, Bente Irene, Acta Chemica Scandinavica, 1993, vol. 47, # 5, p. 532 - 534
  作者：Bols, Mikael、Hansen, Henrik Claus、Smith, Bente Irene

  DOI：——

  日期：——
• Anionic Additions to Glycosyl Iodides:  Highly Stereoselective Syntheses of β <i>C</i>-, <i>N</i>-, and <i>O</i>-Glycosides¹
  作者：Jacquelyn Gervay、Michael J. Hadd

  DOI：10.1021/jo970922t

  日期：1997.10.1

  Classically, glycosyl halides are activated as glycosyl donors by metal chelation under Koenigs-Knorr or Helferich conditions. These reactions often proceed through oxonium formation, and the stereochemical outcome is dictated by the anomeric effect and/or the nature of the protecting group on the C2 hydroxyl. Alternatively, glycosyl halides may undergo direct displacement of the halide by an incoming nucleophile in an S(N)2 mechanism. The latter reaction is far less common, and before this study it was primarily performed with glycosyl bromides. Having recently shown that both alpha and beta glycosyl iodides could be efficiently generated, we embarked upon an investigation of nucleophilic additions to glycosyl iodides. The studies reported herein show that additions of stabilized anions to alpha-glycosyl iodides proceed with inversion of stereochemistry to give beta-glycosides, even in the absence of a C2 participatory group. Glucosyl, galactosyl, and mannosyl iodides were studied, and the combined results indicate that the reactivity of 2,3,4,6-tetra-O-benzyl-alpha-D-galactosyl iodide > 2,3,4,6-tetra-O-benzyl-alpha-D-glucosyl iodide > 2,3,4,6-tetra-O-benzyl-alpha-D-mannosyl iodide. Both the glucosyl and galactosyl iodides are susceptible to E-2 elimination when treated with highly basic anions. In contrast, the mannosyl iodide undergoes substitution to give the 1,2 cis configuration. The overall sequence involves reaction of an anomeric acetate with trimethylsilyl iodide with in vacuo removal of the resulting trimethylsilyl acetate. The iodide is then treated with a nucleophile without further characterization. A variety of nucleophiles were stereoselectively added to the glycosyl halides providing beta-, C-, N-, and O-glycosides.
• Stereoselective synthesis of 1-O-pivaloyl .beta.-D-glucopyranuronic acid
  作者：Mikael Bols

  DOI：10.1021/jo00020a044

  日期：1991.9