[(2R,3R,4S,5R,6S)-3,4,5-trihydroxy-6-(4-methylphenyl)sulfanyloxan-2-yl]methyl 2,2-dimethylpropanoate | 1269658-27-6

• 分子结构分类: 有机化合物 - 有机氧化合物
• 英文名称: [(2R,3R,4S,5R,6S)-3,4,5-trihydroxy-6-(4-methylphenyl)sulfanyloxan-2-yl]methyl 2,2-dimethylpropanoate
• CAS: 1269658-27-6
• 化学式: C₁₈H₂₆O₆S
• 分子量: 370.467
• InChiKey: XHLYFPFMOXKGPW-CWVYHPPDSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  2.1
• 重原子数：
  25
• 可旋转键数：
  6
• 环数：
  2.0
• sp3杂化的碳原子比例：
  0.61
• 拓扑面积：
  122
• 氢给体数：
  3
• 氢受体数：
  7

反应信息

• 作为反应物：
  描述：

  [(2R,3R,4S,5R,6S)-3,4,5-trihydroxy-6-(4-methylphenyl)sulfanyloxan-2-yl]methyl 2,2-dimethylpropanoate 在 吡啶 、 原乙酸三乙酯 作用下， 以 二氯甲烷 、 乙腈 为溶剂， 反应 2.67h， 生成 p-tolyl 2,4-di-O-acetyl-3-O-(chloroacetyl)-6-O-pivaloyl-1-thio-β-D-galactopyranoside
  参考文献：
  名称：

  Aggregation of a Tetrasaccharide Acceptor Observed by NMR: Synthesis of Pentasaccharide Fragments of the Le^aLe^x Tumor-Associated Hexasaccharide Antigen

  摘要：

  We report the synthesis of a tetrasaccharide and two pentasaccharide fragments of the Le(a)Le(x) tumor-associated carbohydrate antigen alpha-L-Fuc-(1 -> 4)-[beta-d-Gal-(1 -> 3)]-beta-d-GlcNAc-(1 -> 3)-beta-d-Gal-(1 -> 4)-[alpha-l-Fuc-(1 -> 3)]-beta-d-GlcNAc-(1 -> OR). The choice of protecting groups permitted a one-step global deprotection (Na/NH3(l)). The protected chlorohexyl glycoside pentasaccharide was the precursor to the hexyl glycoside, to be used as a soluble inhibitor, and the aminohexyl glycoside analogue, to be conjugated to proteins for surface immobilization and immunization experiments. We observed that a linear tetrasaccharide that contained two N-acetylglucosamine residues and a free OH group gave two distinct sets of H-1 NMR signals when the data were acquired in deuterated chloroform. Data acquisition at variable concentrations and variable temperatures suggests that the second set of NMR signals results from aggregation of the tetrasaccharide driven by the formation of intermolecular H-bonds involving the NHAc. While the formation of intra- and intermolecular H-bonds involving N-acetylgucosamine residues has been reported in non-H-bonding solvents, this is, to our knowledge, the first time that these have lead to the appearance of two distinct sets of signals in the NMR spectra. This aggregation may explain the lack of reactivity observed when an attempt is made to glycosylate such an acceptor using non-H-bonding solvents such as dichloromethane.

  DOI：

  10.1021/acs.joc.5b00405
• 作为产物：
  描述：

  [(2R,3S,4S,5R,6S)-3,4,5-triacetyloxy-6-(4-methylphenyl)sulfanyloxan-2-yl]methyl 2,2-dimethylpropanoate 在 甲醇 、 molybdenum(VI) oxychloride 作用下， 反应 168.0h， 以75%的产率得到[(2R,3R,4S,5R,6S)-3,4,5-trihydroxy-6-(4-methylphenyl)sulfanyloxan-2-yl]methyl 2,2-dimethylpropanoate
  参考文献：
  名称：

  Chemoselective deacylation of functionalized esters catalyzed by dioxomolybdenum dichloride

  摘要：

  Among five different oxidometallic species and two Lewis acids investigated, MoO(2)Cl(2) shows the best catalytic and chemoselective activity for the deacylation of esters in methanol at ambient or elevated temperature. Both high efficiency and chemoselectivity were achieved for substrates bearing different ether or ester groups. Acylated mono and disaccharides can also be selectively deacetylated in good yields, leading to useful carbohydrate templates for further synthetic manipulations. (C) 2010 Elsevier Ltd. All rights reserved.

  DOI：

  10.1016/j.tet.2010.12.024