1-deoxy-1-(C-dimethylmalonyl)-2,3,4,6-tetra-O-benzyl-D-glucopyranose | 96689-83-7

• 分子结构分类: 有机化合物 - 有机氧化合物
• 英文名称: 1-deoxy-1-(C-dimethylmalonyl)-2,3,4,6-tetra-O-benzyl-D-glucopyranose
• 英文别名: dimethyl 2-[(2R,3S,4R,5R,6R)-3,4,5-tris(phenylmethoxy)-6-(phenylmethoxymethyl)oxan-2-yl]propanedioate
• CAS: 96689-83-7
• 化学式: C₃₉H₄₂O₉
• 分子量: 654.757
• InChiKey: YHGHXLQSLVCELX-HCAGZTCDSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  5.5
• 重原子数：
  48
• 可旋转键数：
  18
• 环数：
  5.0
• sp3杂化的碳原子比例：
  0.33
• 拓扑面积：
  98.8
• 氢给体数：
  0
• 氢受体数：
  9

反应信息

• 作为产物：
  描述：

  2,3,4,6-四苄基-D-吡喃葡萄糖 在 吡啶 、 15-冠醚-5 、 碘代三甲硅烷 、 sodium hexamethyldisilazane 作用下， 以 二氯甲烷 为溶剂， 反应 9.5h， 生成 1-deoxy-1-(C-dimethylmalonyl)-2,3,4,6-tetra-O-benzyl-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

• C-Glycosidation of pyridyl thioglycosides
  作者：Andrew O. Stewart、Robert M. Williams

  DOI：10.1021/ja00300a036

  日期：1985.7
• 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.