Methyl 2-(3,4,6-tri-O-benzyl-2-deoxy-2-(p-tolylthio)-β-D-glucopyranosyl)-2-methylpropionate

• 分子结构分类: 有机化合物 - 有机氧化合物
• 英文名称: Methyl 2-(3,4,6-tri-O-benzyl-2-deoxy-2-(p-tolylthio)-β-D-glucopyranosyl)-2-methylpropionate
• 英文别名: methyl 2-methyl-2-[(2S,3S,4S,5R,6R)-3-(4-methylphenyl)sulfanyl-4,5-bis(phenylmethoxy)-6-(phenylmethoxymethyl)oxan-2-yl]propanoate
• 化学式: C₃₉H₄₄O₆S
• 分子量: 640.841
• InChiKey: AGDGFZQGXKZGCB-KHKVHWIZSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  7.5
• 重原子数：
  46
• 可旋转键数：
  15
• 环数：
  5.0
• sp3杂化的碳原子比例：
  0.36
• 拓扑面积：
  88.5
• 氢给体数：
  0
• 氢受体数：
  7

反应信息

• 作为反应物：
  描述：

  Methyl 2-(3,4,6-tri-O-benzyl-2-deoxy-2-(p-tolylthio)-β-D-glucopyranosyl)-2-methylpropionate 在 偶氮二异丁腈 、 三正丁基氢锡 作用下， 以 甲苯 为溶剂， 反应 12.0h， 以92%的产率得到methyl 2-(3,4,6-tri-O-benzyl-2-deoxy-β-D-glucopyranosyl)-2-methylpropionate
  参考文献：
  名称：

  Reduction of 2-Arylthio-β-C-D-Glucopyranosides with Different Functional Groups in the Lateral Chain

  摘要：

  [image omitted] 2-Arylthio--C-D-glucopyranosides with a carbonyl or methoxy group in the lateral chain (1 and 2) can be converted to the corresponding 2-deoxy--C-D-glucopyranosides (1a and 2a) using Raney Ni. Reduction of 2-arylthio--C-D-glucopyranosides bearing an ester, methoxy, CN, or C=C moiety in the side chain (3-6) using n-Bu3SnH in the presence of azobisisobutyronitrile (AIBN) provided the corresponding 2-deoxy--C-D-glucopyranosides (3a-6a) without reducing additional functional groups. The application of n-Bu3SnH and AIBN in reaction with 2-arylthio--C-D-glucopyranoside (7) containing a Me3Si group bonded to the carbonyl fragment (7) resulted in the reduction of both the 2-ArS and C=O groups.

  DOI：

  10.1080/00397911.2010.481738
• 作为产物：
  描述：

  4-甲基苯硫氯 、 1-甲氧基-1-(三甲基甲硅氧基)-2-甲基-1-丙烯 、 3,4,6-三苄氧基-D-葡萄烯糖 在 四氯化锡 、 水 、 碳酸氢钠 作用下， 以 二氯甲烷 为溶剂， 反应 1.17h， 生成 Methyl 2-(3,4,6-tri-O-benzyl-2-deoxy-2-(p-tolylthio)-β-D-glucopyranosyl)-2-methylpropionate
  参考文献：
  名称：

  Reduction of 2-Arylthio-β-C-D-Glucopyranosides with Different Functional Groups in the Lateral Chain

  摘要：

  [image omitted] 2-Arylthio--C-D-glucopyranosides with a carbonyl or methoxy group in the lateral chain (1 and 2) can be converted to the corresponding 2-deoxy--C-D-glucopyranosides (1a and 2a) using Raney Ni. Reduction of 2-arylthio--C-D-glucopyranosides bearing an ester, methoxy, CN, or C=C moiety in the side chain (3-6) using n-Bu3SnH in the presence of azobisisobutyronitrile (AIBN) provided the corresponding 2-deoxy--C-D-glucopyranosides (3a-6a) without reducing additional functional groups. The application of n-Bu3SnH and AIBN in reaction with 2-arylthio--C-D-glucopyranoside (7) containing a Me3Si group bonded to the carbonyl fragment (7) resulted in the reduction of both the 2-ArS and C=O groups.

  DOI：

  10.1080/00397911.2010.481738

文献信息

• Highly Selective Formation of a .beta.-C-Glucosidic Bond in the Reactions of ArSCl-Glucal Adducts with Silicon-Containing Nucleophiles
  作者：Irina P. Smoliakova、Ron Caple、Dan Gregory、William A. Smit、Alexander S. Shashkov、Oleg S. Chizhov

  DOI：10.1021/jo00110a027

  日期：1995.3

  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.
• Reduction of 2-Arylthio-<font>β</font>-<i>C</i>-<scp>D</scp>-Glucopyranosides with Different Functional Groups in the Lateral Chain
  作者：Mingming Han、Irina P. Smoliakova

  DOI：10.1080/00397911.2010.481738

  日期：2011.3.28

  [image omitted] 2-Arylthio--C-D-glucopyranosides with a carbonyl or methoxy group in the lateral chain (1 and 2) can be converted to the corresponding 2-deoxy--C-D-glucopyranosides (1a and 2a) using Raney Ni. Reduction of 2-arylthio--C-D-glucopyranosides bearing an ester, methoxy, CN, or C=C moiety in the side chain (3-6) using n-Bu3SnH in the presence of azobisisobutyronitrile (AIBN) provided the corresponding 2-deoxy--C-D-glucopyranosides (3a-6a) without reducing additional functional groups. The application of n-Bu3SnH and AIBN in reaction with 2-arylthio--C-D-glucopyranoside (7) containing a Me3Si group bonded to the carbonyl fragment (7) resulted in the reduction of both the 2-ArS and C=O groups.