1-ethylsulfenyl-3,4,6-tri-O-acetyl-1,2-dideoxy-2-N-tetrachlorophthalimido-β-D-glucopyranoside | 224047-32-9

• 分子结构分类: 有机化合物 - 有机氧化合物
• 英文名称: 1-ethylsulfenyl-3,4,6-tri-O-acetyl-1,2-dideoxy-2-N-tetrachlorophthalimido-β-D-glucopyranoside
• 英文别名: ethyl 3,4,6-tri-O-acetyl-2-deoxy-2-N-tetrachlorophthalimido-1-thio-β-D-glucopyranoside；ethyl 3,4,6-tri-O-acetyl-2-deoxy-2-tetrachlorophthalimido-1-thio-β-D-glucopyranoside；[(2R,3S,4R,5R,6S)-3,4-diacetyloxy-6-ethylsulfanyl-5-(4,5,6,7-tetrachloro-1,3-dioxoisoindol-2-yl)oxan-2-yl]methyl acetate
• CAS: 224047-32-9
• 化学式: C₂₂H₂₁Cl₄NO₉S
• 分子量: 617.288
• InChiKey: FSGUMJQDRYHZQT-DRLSZQQQSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  4.2
• 重原子数：
  37
• 可旋转键数：
  10
• 环数：
  3.0
• sp3杂化的碳原子比例：
  0.5
• 拓扑面积：
  151
• 氢给体数：
  0
• 氢受体数：
  10

反应信息

• 作为反应物：
  描述：

  1-ethylsulfenyl-3,4,6-tri-O-acetyl-1,2-dideoxy-2-N-tetrachlorophthalimido-β-D-glucopyranoside 在 盐酸 、 4-二甲氨基吡啶 、 水 、 间氯过氧苯甲酸 作用下， 以 吡啶 、 二氯甲烷 、 丙酮 为溶剂， 反应 60.25h， 生成 1-(S)-ethylsulfinyl-3,4,6-tri-O-pivaloyl-1,2-dideoxy-2-N-tetrachlorophthalimido-β-D-glucopyranoside
  参考文献：
  名称：

  Highly Diastereoselective Oxidation of 2-Amino-2-deoxy-1-thio-β-d-glucopyranosides:  Synthesis of Imino Sulfinylglycosides

  摘要：

  A synthetic route to imino thioglycosides and to imino sulfinylglycosides has been developed. A detailed study on the diastereoselective oxidation of 2-amino-2-deoxy-1-thio-beta-D-glucopyranosides is reported. It has been shown that the stereochemical outcome of the oxidation is highly dependent on the protective group of the amine function. While the oxidation of iminothioglycosides is slightly diastereoselective (up to 30% de in favor of the R-S sulfoxide), a single isomer is obtained in the case of tetrachloroplithalimido derivatives. The absolute configuration of the sulfinyl glycoside was ascertained by NMR analysis using our recent model on the basis of the exo-anomeric effect corroborated by X-ray crystallography.

  DOI：

  10.1021/jo026519q
• 作为产物：
  描述：

  1,3,4,6-tetra-O-acetyl-2-deoxy-2-tetrachlorophthalimido-α-D-glucopyranoside 在 silver zeolite 、 氢溴酸 、 四氯化钛 、 溶剂黄146 作用下， 以 二氯甲烷 为溶剂， 生成 1-ethylsulfenyl-3,4,6-tri-O-acetyl-1,2-dideoxy-2-N-tetrachlorophthalimido-β-D-glucopyranoside
  参考文献：
  名称：

  Access to tetrachlorophthalimide-protected ethyl 2-amino-2-deoxy-1-thio-β-d-glucopyranosides

  摘要：

  Ethyl 2-deoxy-2-tetrachlorophthalimido-1-thio-beta-D-glucopyranoside (7) was prepared from glucosamine hydrochloride in four steps with a 20-25% overall yield. Formation of 1,3,4,6-tetra-O-acetyl-2-deoxy-2-tetrachlorophthalimido-beta-D-glucopyranoside (5) was found to be crucial for this reaction sequence since the corresponding alpha-1-acetate did not react in Lewis-acid-catalyzed ethylthio glycosidations. Formation of the beta-1-acetate (5) was achieved by treatment of 3,4,6-tri-O-acetyl-2-deoxy-2-tetrachlorophthalimido-alpha-D-glucopyranosol bromide(4) with acetic acid under silver zeolite promotion. This was necessary because conditions normally used for p-l-acetate formation were not tolerated by the tetrachlorophthalimido (TCP) group. (C) 1998 Elsevier Science Ltd. All rights reserved.

  DOI：

  10.1016/s0008-6215(98)00309-7

文献信息

• Conformational Flexibility and Dynamics of Two (1→6)-Linked Disaccharides Related to an Oligosaccharide Epitope Expressed on Malignant Tumour Cells
  作者：Ulrika Olsson、Elin Säwén、Roland Stenutz、Göran Widmalm

  DOI：10.1002/chem.200900507

  日期：2009.9.7

  The conformational flexibility and dynamics of two (1→6)‐linked disaccharides that are related to the action of the glycosyl transferase GnT‐V have been investigated. NMR NOE and T‐ROE spectroscopy experiments, conformation‐dependent coupling constants and molecular dynamics (MD) simulations were used in the analyses. To facilitate these studies, the compounds were synthesised as α‐d‐[6‐13C]‐Manp‐OMe

  研究了与糖基转移酶GnT-V作用有关的两个（1→6）连接的二糖的构象柔韧性和动力学。分析中使用了NMR NOE和T-ROE光谱实验，依赖构象的耦合常数和分子动力学（MD）模拟。为了促进这些研究中，所述化合物合成为α- D- [6- 13 C] -Man p -OMe衍生物，其降低了1 1 H NMR光谱重叠，并促进两个和三个键的确定1 H，1 H，1 H，13 C和13 C，13C耦合常数。对于糖苷的人口分布ω在α-扭转角D-曼p - （1→6）-α- D-曼p -OMe为GT / GG / TG等于45：50：5，而在α- d‐ man p‐ OMe被确定为56：36：8。这是对于β-产生的动态模型D- GLC p NAc-（1→6）-α- D-曼p通过分子动力学模拟采用基于CHARMM-PARM22 / SU01力场是在与实验观察非常好的一致性-OMe 。β‐ d‐ Glc p NAc‐（1→6）‐α‐D-曼p