2,3-di-O-benzoyl-4,6-O-benzylidene-α-D-glucopyranosyl trichloroacetimidate

• 分子结构分类: 有机化合物 - 有机杂环化合物 - 吡喃二恶英
• 英文名称: 2,3-di-O-benzoyl-4,6-O-benzylidene-α-D-glucopyranosyl trichloroacetimidate
• 英文别名: [(2R,4aR,6R,7R,8S,8aR)-7-benzoyloxy-2-phenyl-6-(2,2,2-trichloroethanimidoyl)oxy-4,4a,6,7,8,8a-hexahydropyrano[3,2-d][1,3]dioxin-8-yl] benzoate
• 化学式: C₂₉H₂₄Cl₃NO₈
• 分子量: 620.87
• InChiKey: AIZUDNNEAJEUDO-SUEWFMIISA-N

计算性质

• 辛醇/水分配系数(LogP)：
  6.3
• 重原子数：
  41
• 可旋转键数：
  9
• 环数：
  5.0
• sp3杂化的碳原子比例：
  0.28
• 拓扑面积：
  113
• 氢给体数：
  1
• 氢受体数：
  9

反应信息

• 作为反应物：
  描述：

  双丙酮葡萄糖 、 2,3-di-O-benzoyl-4,6-O-benzylidene-α-D-glucopyranosyl trichloroacetimidate 在 4 A molecular sieve 、 silver trifluoromethanesulfonate 作用下， 以 二氯甲烷 为溶剂， 以88%的产率得到2,3-di-O-benzoyl-4,6-O-benzylidene-β-D-glucopyranosyl-(1->3)-1,2:5,6-di-O-isopropylidene-α-D-glucofuranose
  参考文献：
  名称：

  Silver Triflate. A Mild Alternative Catalyst for Glycosylation Conditions Using Trichloroacetimidates as Glycosyl Donors

  摘要：

  Although trimethylsilyl triflate (TMSOTf) has been widely used to promote glycosyl trichloroacetimidates in oligosaccharide synthesis, silver triflate (AgOTf) was proved to be a mild and in some cases more efficient catalyst in TMSOTf-sensitive glycosylations. Migration and degradation in some specific coupling reactions can be reduced significantly under this alternative glycosylation condition.

  DOI：

  10.1081/car-120025325
• 作为产物：
  描述：

  三氯乙腈 、 4,6-O-benzylidene-2,3-di-O-benzoyl-D-glucopyranose 在 1,8-二氮杂双环[5.4.0]十一碳-7-烯 作用下， 以 二氯甲烷 为溶剂， 反应 3.0h， 生成 2,3-di-O-benzoyl-4,6-O-benzylidene-β-D-glucopyranosyl trichloroacetimidate 、 2,3-di-O-benzoyl-4,6-O-benzylidene-α-D-glucopyranosyl trichloroacetimidate
  参考文献：
  名称：

  Synthesis ofStreptococcus pneumoniae Type 3 Neoglycoproteins Varying in Oligosaccharide Chain Length, Loading and Carrier Protein

  摘要：

  The preparation is described of a range of neoglycoproteins containing synthesised fragments of the capsular polysaccharide of Streptococcus pneumoniae type 3, that is beta-D-GlcpA-(1-->4)-beta-D-Glcp-(1-->O)-(CH2)3NH2 (1), beta-D-Glcp-(1-->3)-beta-D-GlcpA-(1-->4)-beta-D-Glcp-(1-->O)-(CH2)3NH2 (2), and beta-D-GlcpA-(1-->4)-beta-D-Glcp-(1-->3)-beta-D-GlcpA-(1-->4)-beta-D-Glcp-(1-->O)-(CH4)NH2 (3). A blockwise approach was developed for the synthesis of the protected carbohydrate chains, in which the carboxylic groups were introduced prior to deprotection by selective oxidation of HO-6 in the presence of HO-4 by using TEMPO (2,2,6,6-tetramethyl-1-piperidinyloxy radical). After deprotection, the 3-aminopropyl spacer of the fragments was elongated with diethyl squarate (3,4-diethoxy-3-cyclobutene-1,2-dione) and the elongated oligosaccharides were conjugated to CRM197 (cross-reacting material of diphtheria toxin), KLH (keyhole limpet hemocyanin) or TT (tetanus toxoid). The resulting neoglycoconjugates varied in oligosaccharide chain length, oligosaccharide loading and protein carrier. These well-defined conjugates are ideal probes for evaluating the influence of the different structural parameters in immunological tests.

  DOI：

  10.1002/1521-3765(20011015)7:20<4411::aid-chem4411>3.0.co;2-t

文献信息

• 一种血清型Ⅷ型B族链球菌寡糖片段及其制备方法与应用
  申请人：山东大学

  公开号：CN113292615B

  公开（公告）日：2022-06-28

  本发明涉及一种血清型Ⅷ型B族链球菌寡糖片段及其制备方法与应用。本发明制备的寡糖片段为血清型Ⅷ型B族链球菌不同还原端重复片段，是以各种保护的单糖模块为原料，通过收敛式糖基化组装依次进行糖苷化反应来制备得到的，其中的寡糖片段的各还原端吡喃糖基的C‑1位是由氨基烷烃链修饰，可与蛋白缀合进而制备成寡糖蛋白缀合物，然后进行相关免疫学研究。本发明的制备方法设计合理，可操作性强，分离简单，产品收率高，纯度好。通过合成不同还原端的多糖重复片段以进行免疫学研究，对于研发相应的血清型Ⅷ型B族链球菌糖类疫苗具有重要意义。
• Regioselective Benzylation of 2-Deoxy-2-aminosugars using Crown Ethers: Application to a Shortened Synthesis of Hyaluronic Acid Oligomers
  作者：Chinmoy Mukherjee、Lin Liu、Nicola L. B. Pohl

  DOI：10.1002/adsc.201400269

  日期：2014.7.7

  bromide, sodium hydroxide and 15‐crown‐5 in tetrahydrofuran is shown to be an efficient method for installing benzyl groups at both the 4‐ and 6‐positions regioselectively directly from peracetylated N‐trichloroacetyl‐protected glucosamine and galactosamine. Application of this benzylation strategy proved to significantly shorten the synthetic route to hyaluronic acid tetra‐ and hexamers.

  在四氢呋喃中结合使用溴化苄，氢氧化钠和15-crown-5是一种有效的方法，可直接从过乙酰化的N-三氯乙酰基保护的葡糖胺和半乳糖胺中区域选择性地直接在4位和6位安装苄基。实践证明，这种苄基化策略的应用大大缩短了合成透明质酸四聚体和六聚体的途径。
• Silver Triflate. A Mild Alternative Catalyst for Glycosylation Conditions Using Trichloroacetimidates as Glycosyl Donors
  作者：Guohua Wei、Guofeng Gu、Yuguo Du

  DOI：10.1081/car-120025325

  日期：2003.1.10

  Although trimethylsilyl triflate (TMSOTf) has been widely used to promote glycosyl trichloroacetimidates in oligosaccharide synthesis, silver triflate (AgOTf) was proved to be a mild and in some cases more efficient catalyst in TMSOTf-sensitive glycosylations. Migration and degradation in some specific coupling reactions can be reduced significantly under this alternative glycosylation condition.
• Synthesis ofStreptococcus pneumoniae Type 3 Neoglycoproteins Varying in Oligosaccharide Chain Length, Loading and Carrier Protein
  作者：Dirk J. Lefeber、Johannis P. Kamerling、Johannes F. G. Vliegenthart

  DOI：10.1002/1521-3765(20011015)7:20<4411::aid-chem4411>3.0.co;2-t

  日期：2001.10.15

  The preparation is described of a range of neoglycoproteins containing synthesised fragments of the capsular polysaccharide of Streptococcus pneumoniae type 3, that is beta-D-GlcpA-(1-->4)-beta-D-Glcp-(1-->O)-(CH2)3NH2 (1), beta-D-Glcp-(1-->3)-beta-D-GlcpA-(1-->4)-beta-D-Glcp-(1-->O)-(CH2)3NH2 (2), and beta-D-GlcpA-(1-->4)-beta-D-Glcp-(1-->3)-beta-D-GlcpA-(1-->4)-beta-D-Glcp-(1-->O)-(CH4)NH2 (3). A blockwise approach was developed for the synthesis of the protected carbohydrate chains, in which the carboxylic groups were introduced prior to deprotection by selective oxidation of HO-6 in the presence of HO-4 by using TEMPO (2,2,6,6-tetramethyl-1-piperidinyloxy radical). After deprotection, the 3-aminopropyl spacer of the fragments was elongated with diethyl squarate (3,4-diethoxy-3-cyclobutene-1,2-dione) and the elongated oligosaccharides were conjugated to CRM197 (cross-reacting material of diphtheria toxin), KLH (keyhole limpet hemocyanin) or TT (tetanus toxoid). The resulting neoglycoconjugates varied in oligosaccharide chain length, oligosaccharide loading and protein carrier. These well-defined conjugates are ideal probes for evaluating the influence of the different structural parameters in immunological tests.