dicyclohexylmethyl 2,3,4,6-tetra-O-benzyl-1-thio-α-D-galactopyranoside | 911684-28-1

• 分子结构分类: 有机化合物 - 有机氧化合物
• 英文名称: dicyclohexylmethyl 2,3,4,6-tetra-O-benzyl-1-thio-α-D-galactopyranoside
• CAS: 911684-28-1
• 化学式: C₄₇H₅₈O₅S
• 分子量: 735.041
• InChiKey: ASBQPTOTIFBBCO-GOAQLSPTSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  10.95
• 重原子数：
  53.0
• 可旋转键数：
  17.0
• 环数：
  7.0
• sp3杂化的碳原子比例：
  0.49
• 拓扑面积：
  46.15
• 氢给体数：
  0.0
• 氢受体数：
  6.0

反应信息

• 作为反应物：
  描述：

  dicyclohexylmethyl 2,3,4,6-tetra-O-benzyl-1-thio-α-D-galactopyranoside 、 3,4,6-tri-O-acetyl-2-azido-2-deoxy-D-galactopyranosyl trichloroacetimidate 在 三氟甲磺酸三甲基硅酯 作用下， 以 二氯甲烷 为溶剂， 以15%的产率得到dicyclohexylmethyl 2-azido-3,4,6-tri-O-acetyl-2-deoxyl-1-α-thio-D-galactopyranoside
  参考文献：
  名称：

  Mechanistic Studies and Methods To Prevent Aglycon Transfer of Thioglycosides

  摘要：

  Thioglycosides have been employed extensively for the synthesis of complex oligosaccharides, carbohydrate libraries, and mimetics of O-glycosides. While very useful, aglycon transfer is a problematic side reaction with thioglycosides. In this paper, a series of mechanistic studies are described. The aglycon transfer process is shown to affect both armed and disarmed thioglycosides, cause anomerization of the carbon-sulfur bond of a thioglycoside, and destroy the product of a glycosylation reaction. The results indicate that the aglycon transfer process can be a major problem for a wide range of thioglycosides. This side reaction is especially important to consider when carrying out complex reactions such as solid-phase glycosylations, one-pot or orthogonal multicomponent glycosylations, and construction of carbohydrate libraries. To prevent transfer, a number of modified aglycons were examined. The 2,6-dimethylphenyl ( DMP) aglycon was found to effectively block transfer in a variety of model studies and glycosylation reactions. The DMP group can be installed in one step from a commercially available thiol ( 2,6-dimethylthiophenol) and is useable as a glycosyl donor. On the basis of these features, the DMP group is proposed as a convenient and improved aglycon for thioglycosides.

  DOI：

  10.1021/ja063247q
• 作为产物：
  描述：

  Acetic acid (2R,3S,4S,5R,6R)-3,5-diacetoxy-2-acetoxymethyl-6-dicyclohexylmethylsulfanyl-tetrahydro-pyran-4-yl ester 在 sodium methylate 、 sodium hydride 作用下， 以 甲醇 、 N,N-二甲基甲酰胺 为溶剂， 反应 2.0h， 生成 dicyclohexylmethyl 2,3,4,6-tetra-O-benzyl-1-thio-α-D-galactopyranoside
  参考文献：
  名称：

  Mechanistic Studies and Methods To Prevent Aglycon Transfer of Thioglycosides

  摘要：

  Thioglycosides have been employed extensively for the synthesis of complex oligosaccharides, carbohydrate libraries, and mimetics of O-glycosides. While very useful, aglycon transfer is a problematic side reaction with thioglycosides. In this paper, a series of mechanistic studies are described. The aglycon transfer process is shown to affect both armed and disarmed thioglycosides, cause anomerization of the carbon-sulfur bond of a thioglycoside, and destroy the product of a glycosylation reaction. The results indicate that the aglycon transfer process can be a major problem for a wide range of thioglycosides. This side reaction is especially important to consider when carrying out complex reactions such as solid-phase glycosylations, one-pot or orthogonal multicomponent glycosylations, and construction of carbohydrate libraries. To prevent transfer, a number of modified aglycons were examined. The 2,6-dimethylphenyl ( DMP) aglycon was found to effectively block transfer in a variety of model studies and glycosylation reactions. The DMP group can be installed in one step from a commercially available thiol ( 2,6-dimethylthiophenol) and is useable as a glycosyl donor. On the basis of these features, the DMP group is proposed as a convenient and improved aglycon for thioglycosides.

  DOI：

  10.1021/ja063247q