1-Phenyl-2-(3,4,6-tri-O-benzyl-2-deoxy-2-(p-tolylthio)-β-D-glucopyranosyl)-1-oxoethane

• 分子结构分类: 有机化合物 - 有机氧化合物
• 英文名称: 1-Phenyl-2-(3,4,6-tri-O-benzyl-2-deoxy-2-(p-tolylthio)-β-D-glucopyranosyl)-1-oxoethane
• 英文别名: 2-[(2S,3S,4S,5R,6R)-3-(4-methylphenyl)sulfanyl-4,5-bis(phenylmethoxy)-6-(phenylmethoxymethyl)oxan-2-yl]-1-phenylethanone
• 化学式: C₄₂H₄₂O₅S
• 分子量: 658.858
• InChiKey: LHBAFNWGRMKFFO-PGRNDEIQSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  8.1
• 重原子数：
  48
• 可旋转键数：
  15
• 环数：
  6.0
• sp3杂化的碳原子比例：
  0.26
• 拓扑面积：
  79.3
• 氢给体数：
  0
• 氢受体数：
  6

反应信息

• 作为产物：
  描述：

  1-苯基-1-三甲基硅氧乙烯 、 (2R,3R,4S)-3,4-Bis-benzyloxy-2-benzyloxymethyl-6-chloro-5-p-tolylsulfanyl-tetrahydro-pyran 在 四氯化锡 作用下， 以 二氯甲烷 为溶剂， 反应 0.5h， 生成 1-Phenyl-2-(3,4,6-tri-O-benzyl-2-deoxy-2-(p-tolylthio)-α-D-mannopyranosyl)-1-oxoethane 、 1-Phenyl-2-(3,4,6-tri-O-benzyl-2-deoxy-2-(p-tolylthio)-β-D-glucopyranosyl)-1-oxoethane
  参考文献：
  名称：

  Highly Selective Formation of a .beta.-C-Glucosidic Bond in the Reactions of ArSCl-Glucal Adducts with Silicon-Containing Nucleophiles

  摘要：

  2-(Arylthio)-2-deoxyglucosyl chlorides, which are easily prepared as a mixture of stereoisomers upon the Ad(E) reaction of ArSCl with tri-O-benzyl-D-glucal, upon treatment with a Lewis acid catalyst can be transformed into cationoid intermediates, presumably episulfonium ions. The latter were shown to be efficient electrophiles capable of alkylating various Si-containing nucleophiles such as TMSCN, allyltrimethylsilane, TMS; enol ethers, and ketene acetals with formation of the corresponding. 2-deoxy-2-(arylthio)-C-glucosides in-preparatively acceptable yields. The final outcome of the reaction corresponds to a net trans-addition of ArS and carbon nucleophile moieties across the double bond of the starting glucal. The stereofacial selectivity of this addition is sensitive to variations in the reaction conditions but generally a below-plane attack is preferable. A highly selective formation of the beta-C-glucosidic bond (ratio of beta-gluco:alpha-manno isomers up to 19:1) can be achieved if the coupling is carried out in CH2Cl2 solution. Thus, the reaction might serve as a convenient method for the synthesis of diverse 2-deoxy-2-(arylthio)-beta-C-glucosides containing aliphatic, cycloaliphatic, or aromatic residues and functional groups like carbonyl, carboxyl, or the double bond.

  DOI：

  10.1021/jo00110a027