methyl 4-azido-2-O-benzyl-4,6-dideoxy-α-D-mannopyranoside | 121803-78-9

• 分子结构分类: 有机化合物 - 有机氧化合物
• 英文名称: methyl 4-azido-2-O-benzyl-4,6-dideoxy-α-D-mannopyranoside
• 英文别名: (2S,3S,4S,5S,6R)-5-azido-2-methoxy-6-methyl-3-phenylmethoxyoxan-4-ol
• CAS: 121803-78-9
• 化学式: C₁₄H₁₉N₃O₄
• 分子量: 293.323
• InChiKey: NJWFNXBLKYYKER-CYDRSHDDSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  2.0
• 重原子数：
  21.0
• 可旋转键数：
  5.0
• 环数：
  2.0
• sp3杂化的碳原子比例：
  0.57
• 拓扑面积：
  96.68
• 氢给体数：
  1.0
• 氢受体数：
  5.0

反应信息

• 作为反应物：
  描述：

  methyl 4-azido-2-O-benzyl-4,6-dideoxy-α-D-mannopyranoside 在 光气 、 sodium tetrahydroborate 、 二甲基亚砜 、 三乙胺 作用下， 以 乙醇 、 二氯甲烷 、 水 为溶剂， 反应 1.0h， 生成 甲基 4-叠氮基-4,6-二脱氧吡喃甘露糖苷
  参考文献：
  名称：

  合成探索D-过胺的3-脱氧-3-氟衍生物。

  摘要：

  根据文献的先例，尝试了通过4-甲基叠氮基-2-O-苄基-4的氟化制备甲基4-叠氮基-3,4,6-三苯氧基-3-氟代-α-D-甘露吡喃糖苷（18）。 ，6-二脱氧-α-D-altropyranoside与二乙基氨基三氟化硫（DAST）。与预期相反，该反应在氟化位点处保持构型发生，从而产生甲基4-叠氮基-2-O-苄基-3,4,6-三苯氧基-3-氟代-α-D-萘并吡喃糖苷。用DAST处理甲基4-叠氮基-2-O-苄基-4,6-二脱氧-α-D-阿洛吡喃糖苷（8）或其2-（对甲氧基苄基）类似物9导致氟化反应，位置上的构型反转如图3所示，分别得到相应的3-脱氧-3-氟吡喃葡萄糖苷10和11。因此，化合物11由11通过在O-2处进行对-甲氧基苄基化而制备，然后在所得的甲基4-叠氮基-3,4,6-三苯氧基-3-氟-α-D-吡喃葡萄糖苷中的C-2处的构型反转。18（19）的2-O-甲基类似物是通过18的甲基化

  DOI：

  10.1016/s0008-6215(01)00188-4
• 作为产物：
  描述：

  methyl 4-azido-4-deoxy-2,3-O-isopropylidene-α-D-rhamnopyranoside 在 甲醇 、 四丁基溴化铵 、 乙酰氯 、 sodium hydroxide 作用下， 以 二氯甲烷 为溶剂， 生成 methyl 4-azido-2-O-benzyl-4,6-dideoxy-α-D-mannopyranoside
  参考文献：
  名称：

  使用氟化类似物研究自由基 S-腺苷-L-甲硫氨酸酶 DesII 的机理

  摘要：

  DesII 是一种自由基 S-腺苷-L-甲硫氨酸 (SAM) 酶，根据其 TDP-糖底物的性质，可以充当脱氨酶或脱氢酶。先前的工作表明底物衍生的、以 C3 为中心的 α-羟烷基自由基是催化过程中的关键中间体。尽管α-羟烷基的去质子化已被证明对于脱氢很重要，但对于脱氨反应的过程知之甚少。为了研究 C3 羟基在脱氨过程中所起的作用，制备了两种底物的 3-氘-3-氟类似物，并用 DesII 进行了表征。在这两种情况下都没有观察到脱氨或氧化作用；然而，在这两种情况下，氘都在底物类似物和 SAM 之间有效交换。这些结果意味着 C3 羟基在这两个反应中都起着关键作用，从而反对脱氨的 1,2-迁移机制，并且当正向分配受到抑制时，SAM 的均裂伴随着 H 原子从底物中提取，很容易可逆。

  DOI：

  10.1021/jacs.5b02545

文献信息

• Synthetic glycoconjugates characterize the fine specificity of Brucella A and M monoclonal antibodies
  作者：Satadru Sekhar Mandal、N. Vijaya Ganesh、Joanna M. Sadowska、David R. Bundle

  DOI：10.1039/c7ob00445a

  日期：——

  The dominant cell wall antigen of Brucella bacteria is the O-polysaccharide component of the smooth lipopolysaccharide. Infection by various Brucella biovars causes abortions and infertility in a wide range of domestic and wild animals and debilitating disease in humans. Diagnosis relies on the detection of antibodies to the A and M antigens expressed in the O-polysaccharide. This molecule is a homopolymer

  布鲁氏菌细菌的主要细胞壁抗原是光滑脂多糖的O-多糖成分。各种布鲁氏菌生物变种的感染会导致各种家畜和野生动物的流产和不育，并导致人类衰弱的疾病。诊断依赖于针对O-多糖中表达的A和M抗原的抗体的检测。该分子是稀有单糖4-甲酰胺基-4,6-二脱氧-D-甘露吡喃糖（Rha4NFo）的均聚物。A表位是由均匀的α1,2连接的内部聚合物序列产生的，该序列由限定M抗原的独特的四糖序列所覆盖。唯一的寡糖只能通过化学合成获得，并通过牛血清白蛋白的还原性和非还原性残基揭示了精细特异性的结构基础，该特异性可以区分这些密切相关的A和M表位。推断所有这三种M特异性单克隆抗体（mAb）具有在两端开放的凹槽型结合位点，并将α1,3连接的Rha4NFo二糖识别为三糖表位的一部分，在两个mAb中包括末端Rha4NFo残基。这些抗体之一的结合位点足够大，可以结合多达六个Rha4NFo残基，并且涉及对α1,2连接的Rha4NFo
• Synthesis of specifically deoxygenated analogues of the methyl α-glycoside of the intracatenary monosaccharide repeating unit of the O-polysaccharide of Vibrio cholerae O:1
  作者：Makoto Gotoh、Pavol Kováč

  DOI：10.1016/0008-6215(94)00319-b

  日期：1995.3

  which was deoxygenated via the corresponding 3-O-(imidazol-1-ylthiocarbonyl) derivative. Subsequent catalytic debenzylation gave the deoxy compound (24). In an alternative synthesis, which is also generally useful for the preparation of 4-N-acyl-3-deoxy derivatives of 1, methyl 4-azido-4,6-dideoxy-alpha-D-mannopyranoside was converted through a series of transformations into methyl 4-amino-2-O-benzyl-3

  用γ-丁内酯处理甲基α-D-过高胺（1），得到甲基4,6-dideoxy-4-（3-deoxy-L-glycero-tetronamido）-alpha-D-mannopyranos ide的2'-deoxy类似物（13），霍乱弧菌O：1的O-多糖的链内单糖重复单元的甲基α-糖苷。通过4，-氯-脱氧前体的氢解获得类似的4'-脱氧衍生物，所述前体是通过对甲基2,3-二-O-苄基-4-（2-O-苄基-3-脱氧-L-甘油）进行氯化获得的。 -四氢酰胺基）-4,6-d脱氧-α-D-甘露吡喃糖苷与DMF中的甲磺酰氯 为了获得13的3-脱氧类似物，将甲基4-氨基-2-O-苄基-4,6-二脱氧-3-Op-甲氧基-苄基-α-D-甘露吡喃糖苷转化为甲基2-O-苄基-4,6-二脱氧-4-（2,4-二-O-苄基-3-脱氧-L-甘油-四氢呋喃）-α-D-甘露吡喃糖苷，经由相应的3-O-（咪唑-1-基硫代羰基）衍生
• Molecular Recognition of <i>Brucella</i> A and M Antigens Dissected by Synthetic Oligosaccharide Glycoconjugates Leads to a Disaccharide Diagnostic for Brucellosis
  作者：N. Vijaya Ganesh、Joanna M. Sadowska、Susmita Sarkar、Laurence Howells、John McGiven、David R. Bundle

  DOI：10.1021/ja5081184

  日期：2014.11.19

  The cell wall O-polysaccharides of pathogenic Brucella species are homopolymers of the rare sugar 4,6-dideoxy-4-formamido-alpha-D-mannopyranose. Despite the apparent simplicity of the polysaccharide it appears to be a "block copolymer" composed of A and M polysaccharide sequences expressed as a single molecule. The simultaneous presence of both in the cell wall has complicated the understanding of the molecular recognition of these antigens by antibodies present in the serum of infected animals and humans and by monoclonal antibodies. Since presumptive diagnosis of brucellosis, a serious disease in domestic livestock, wild animals, and humans, is based on detection of these antibodies it is important to separate the two antigenic epitopes, one of which is also found in other bacteria. Chemical synthesis provides the only means to achieve this outcome. A series of six oligosaccharides from di to hexasaccharides 1-6 were synthesized and conjugated to proteins to provide glycoconjugate antigens and conjugate vaccines. These chemically defined antigens identified the M antigenic determinant and provided a structural basis for understanding the fine specificity of monoclonal and polyclonal antibodies that bind the M antigen. This resulted in the discovery of a disaccharide that shows considerable potential as an unambiguous diagnostic antigen for detecting brucellosis in humans and animals and two hexasaccharide conjugate vaccine candidates that produce high levels of O-polysaccharide specific antibodies in mice.
• Peters, Thomas; Bundle, David R., Canadian Journal of Chemistry, 1989, vol. 67, p. 497 - 502
  作者：Peters, Thomas、Bundle, David R.

  DOI：——

  日期：——
• Synthesis of spacer-equipped di-, tri-, and the tetrasaccharide fragments of the deacetylated O-PS1 of Citrobacter gillenii O9a,9b, and a related pentasaccharide
  作者：Rina Saksena、Anatoli Chernyak、Pavol Kováč

  DOI：10.1016/j.carres.2008.03.037

  日期：2008.7

  The title rhamnooligosaccharides [alpha-D-Rhap4NAc-(1 -> 3)-O(-D-Rhap4NAc-1-O-(CH2)(5)COOMe, alpha-D-Rhap4NAc-(1 -> 3)-alpha-D-Rhap4NAc-(1 3)-alpha-D-Rhap4NAc-1-O-(CH2)(5)COOMe, alpha-D-Rhap4NAc-(1 -> 2)-alpha-D-Rhap4NAc-(1 -> 3)-alpha-D-Rhap4NAc-(1 -> 3)-alpha-D-Rhap4NAc-1-O-(CH2)(5)COOMe, and alpha-D-Rhap4NAc-(1 -> 3)-alpha-D-Rhap4NAc-(1-2)-(alpha-D-Rhap4NAc-(1 -> 3)-alpha-D-Rhap4NAc(1 -> 3)-alpha-D-Rhap4NAc-1-O-(CH2)(5)COOMe] were synthesized in a stepwise fashion from 5-methoxycarbonylpentyl 4-azido-4, 6-dideoxy-2-O-benzyl-alpha-D-mannopyranoside and orthogonally protected 1-thioglycoside glycosyl donors. The amorphous, final products were fully characterized as corresponding per-O-acetyl derivatives. Published by Elsevier Ltd.