2,6-di-O-benzyl-4-O-para-bromobenzyl-7-O-(tert-butyldiphenylsilyl)-L-glycero-D-manno-heptopyrano-1,5-lactone | 1429492-48-7

• 分子结构分类: 有机化合物 - 苯类化合物 - 苯和取代衍生物
• 英文名称: 2,6-di-O-benzyl-4-O-para-bromobenzyl-7-O-(tert-butyldiphenylsilyl)-L-glycero-D-manno-heptopyrano-1,5-lactone
• CAS: 1429492-48-7
• 化学式: C₄₄H₄₇BrO₇Si
• 分子量: 795.842
• InChiKey: HNDSJKHQEUFUHU-SRWPCTQNSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  7.37
• 重原子数：
  53.0
• 可旋转键数：
  15.0
• 环数：
  6.0
• sp3杂化的碳原子比例：
  0.3
• 拓扑面积：
  83.45
• 氢给体数：
  1.0
• 氢受体数：
  7.0

反应信息

• 作为反应物：
  描述：

  2,6-di-O-benzyl-4-O-para-bromobenzyl-7-O-(tert-butyldiphenylsilyl)-L-glycero-D-manno-heptopyrano-1,5-lactone 在 4-二甲氨基吡啶 、 lithium tri-t-butoxyaluminum hydride 、 N,N'-二异丙基碳二亚胺 作用下， 以 四氢呋喃 、 二氯甲烷 为溶剂， 反应 2.0h， 生成 7-O-tert-butyldiphenylsilyl-2,6-di-O-benzyl-3-O-levulinoyl-4-O-para-bromobenzyl-L-glycero-D-manno-heptopyranosyl levulinoate
  参考文献：
  名称：

  Diversity-oriented Synthesis of Inner Core Oligosaccharides of the Lipopolysaccharide of Pathogenic Gram-negative Bacteria

  摘要：

  Lipopolysaccharide (LPS) is a potent virulence factor of pathogenic Gram-negative bacteria. To better understand the role of L,PS in host-pathogen interactions and to elucidate the antigenic and immunogenic properties of LPS inner core region, a collection of well-defined L-glycero-D-manno-heptose (Hep) and 3-deoxy-alpha-D-manno-oct-2-ulosonic acid (Kdo)-containing inner core oligosaccharides is required. To address this need, we developed a diversity-oriented approach based on a common orthogonal protected disaccharide Hep-Kdo. Utilizing this new approach, we synthesized a range of LPS inner core oligosaccharides from a variety of pathogenic bacteria including Y. pestis, H. influenzae, and Proteus that cause plague, meningitis, and severe wound infections, respectively. Rapid access to these highly branched core oligosaccharides relied on elaboration of the disaccharide Hep-Kdo core as basis for the elongation with various flexible modules including unique Hep and 4-amino-4-deoxy-beta-L-arabinose (Ara4N) monosaccharides and branched Hep-Hep disaccharides. A regio- and stereoselective glycosylation of Kdo 7,8-diol was key to selective installation of the Ara4N moiety at the 8-hydroxyl group of Kdo moiety of the Hep-Kdo disaccharide. The structure of the LPS inner core oligosaccharides was confirmed by comparison of H-1 NMR spectra of synthetic antigens and isolated fragments. These synthetic LPS core oligosaccharides can be covalently bound to carrier proteins via the reducing end pentyl amine linker, to explore their antigenic and immunogenic properties as well as potential applications such as diagnostic tools and vaccines.

  DOI：

  10.1021/ja401164s
• 作为产物：
  描述：

  6-O-benzyl-4-O-para-bromobenzyl-7-O-tert-butyldiphenylsilyl-L-glycero-D-manno-heptopyrano-1,5-lactone 、 溴甲苯 在 silver(l) oxide 作用下， 以 二氯甲烷 为溶剂， 反应 0.5h， 以70%的产率得到2,6-di-O-benzyl-4-O-para-bromobenzyl-7-O-(tert-butyldiphenylsilyl)-L-glycero-D-manno-heptopyrano-1,5-lactone
  参考文献：
  名称：

  Diversity-oriented Synthesis of Inner Core Oligosaccharides of the Lipopolysaccharide of Pathogenic Gram-negative Bacteria

  摘要：

  Lipopolysaccharide (LPS) is a potent virulence factor of pathogenic Gram-negative bacteria. To better understand the role of L,PS in host-pathogen interactions and to elucidate the antigenic and immunogenic properties of LPS inner core region, a collection of well-defined L-glycero-D-manno-heptose (Hep) and 3-deoxy-alpha-D-manno-oct-2-ulosonic acid (Kdo)-containing inner core oligosaccharides is required. To address this need, we developed a diversity-oriented approach based on a common orthogonal protected disaccharide Hep-Kdo. Utilizing this new approach, we synthesized a range of LPS inner core oligosaccharides from a variety of pathogenic bacteria including Y. pestis, H. influenzae, and Proteus that cause plague, meningitis, and severe wound infections, respectively. Rapid access to these highly branched core oligosaccharides relied on elaboration of the disaccharide Hep-Kdo core as basis for the elongation with various flexible modules including unique Hep and 4-amino-4-deoxy-beta-L-arabinose (Ara4N) monosaccharides and branched Hep-Hep disaccharides. A regio- and stereoselective glycosylation of Kdo 7,8-diol was key to selective installation of the Ara4N moiety at the 8-hydroxyl group of Kdo moiety of the Hep-Kdo disaccharide. The structure of the LPS inner core oligosaccharides was confirmed by comparison of H-1 NMR spectra of synthetic antigens and isolated fragments. These synthetic LPS core oligosaccharides can be covalently bound to carrier proteins via the reducing end pentyl amine linker, to explore their antigenic and immunogenic properties as well as potential applications such as diagnostic tools and vaccines.

  DOI：

  10.1021/ja401164s