allyl 6-O-tert-butyldiphenylsilyl-α-D-mannopyranoside | 182187-95-7

• 分子结构分类: 有机化合物 - 有机氧化合物
• 英文名称: allyl 6-O-tert-butyldiphenylsilyl-α-D-mannopyranoside
• 英文别名: (2R,3S,4S,5S,6S)-2-[[tert-butyl(diphenyl)silyl]oxymethyl]-6-prop-2-enoxyoxane-3,4,5-triol
• CAS: 182187-95-7
• 化学式: C₂₅H₃₄O₆Si
• 分子量: 458.627
• InChiKey: IDSPEJNJMQTLCE-DJCPXJLLSA-N

物化性质

• 沸点：
  549.428±50.00 °C(Press: 760.00 Torr)(predicted)
• 密度：
  1.183±0.10 g/cm3(Temp: 25 °C; Press: 760 Torr)(predicted)

计算性质

• 辛醇/水分配系数(LogP)：
  1.57
• 重原子数：
  32
• 可旋转键数：
  9
• 环数：
  3.0
• sp3杂化的碳原子比例：
  0.44
• 拓扑面积：
  88.4
• 氢给体数：
  3
• 氢受体数：
  6

反应信息

• 作为反应物：
  描述：

  allyl 6-O-tert-butyldiphenylsilyl-α-D-mannopyranoside 在 吡啶 、 sodium tetrahydroborate 、 戴斯-马丁氧化剂 、 对甲苯磺酸 作用下， 以 甲醇 、 二氯甲烷 、 1,2-二氯乙烷 为溶剂， 反应 4.5h， 生成
  参考文献：
  名称：

  来自 d-甘露糖的 6-Amino-2,6-dideoxy-α-Kdo 的全合成。

  摘要：

  3-脱氧d -甘露-辛-2-糖酸（KDO）生物合成途径是在抗菌药物发现有希望的靶点。在此，我们报告了 6-氨基-2,6-双脱氧-α-Kdo 在 15 个步骤中从d-甘露糖作为 Kdo 加工酶的潜在抑制剂的全合成。合成序列的关键步骤包括用于双碳链同源化的 Horner-Wadsworth-Emmons 反应，然后是 6 -exo-trig Pd 催化的还原环化或串联 Staudinger/aza-Wittig 反应，同时伴随 α-亚氨基酯还原，使类似 Kdo 的六元氮杂环的α-立体选择性形成成为可能。

  DOI：

  10.1021/acs.orglett.0c01847
• 作为产物：
  描述：

  甘露糖 在 咪唑 、 乙酰氯 作用下， 以 N,N-二甲基甲酰胺 为溶剂， 反应 21.0h， 生成 allyl 6-O-tert-butyldiphenylsilyl-α-D-mannopyranoside
  参考文献：
  名称：

  来自 d-甘露糖的 6-Amino-2,6-dideoxy-α-Kdo 的全合成。

  摘要：

  3-脱氧d -甘露-辛-2-糖酸（KDO）生物合成途径是在抗菌药物发现有希望的靶点。在此，我们报告了 6-氨基-2,6-双脱氧-α-Kdo 在 15 个步骤中从d-甘露糖作为 Kdo 加工酶的潜在抑制剂的全合成。合成序列的关键步骤包括用于双碳链同源化的 Horner-Wadsworth-Emmons 反应，然后是 6 -exo-trig Pd 催化的还原环化或串联 Staudinger/aza-Wittig 反应，同时伴随 α-亚氨基酯还原，使类似 Kdo 的六元氮杂环的α-立体选择性形成成为可能。

  DOI：

  10.1021/acs.orglett.0c01847

文献信息

• An efficient approach to partially O-methylated α-D-mannopyranosides using bis-tert-butyldiphenylsilyl ethers as intermediates
  作者：MaSelma Arias-Pérez、MaJesús Santos

  DOI：10.1016/0040-4020(96)00600-x

  日期：1996.8

  Differential migratory aptitudes of secondary tert-butyldiphenylsilyl (TBDPS) groups have been observed for the bis-silylated derivatives of methyl and allyl α-D-mannopyranosides under several basic media. A remarkable variation of the selectivity in the migration of the TBDPS group at position 3 (O-3 → O-2 versus O-3 → O-4) was found by changing the hardness of the base and reaction conditions. This

  在几种基本介质下，已观察到仲叔丁基二苯基甲硅烷基（TBDPS）的甲基和烯丙基α-D-甘露吡喃糖苷的双甲硅烷基化衍生物具有不同的迁移能力。通过改变碱的硬度和反应条件，发现TBDPS基团在位置3迁移的选择性有显着变化（O-3→O-2对O-3→O-4）。此行为是针对3,6-，2,6-和4,6-双-TBDPS醚3-5a，b（用于制备其他O取代的衍生物的通用中间体）的实际合成。它们成功地转化为甲基和烯丙基的2,4-，3,4-和2,3-二-O-甲基α-D-甘露吡喃糖苷（10-12a，b）。
• A Bioactive Synthetic Outer‐Core Oligosaccharide Derived from a <i>Klebsiella pneumonia</i> Lipopolysaccharide for Bacteria Recognition
  作者：Dushen Chen、Akhilesh K. Srivastava、Justyna Dubrochowska、Lin Liu、Tiehai Li、Joseph P. Hoffmann、Jay K. Kolls、Geert‐Jan Boons

  DOI：10.1002/chem.202203408

  日期：——

  A chemical synthesised outer core tetra- and pentasaccharide derived from the lipopolysaccharide of K. pneumoniae conjugated to the carrier proteins CRM197 and BSA elicited in mice antibodies that recognized isolated LPS as well as various strains of K. pneumoniae demonstrating they can induce relevant antigenic responses.

  化学合成的外核四糖和五糖源自肺炎克雷伯菌的脂多糖，与载体蛋白 CRM 197和 BSA 结合，在小鼠体内引发识别分离的 LPS 以及各种肺炎克雷伯菌菌株的抗体，证明它们可以诱导相关的抗原反应。
• Synthesis of an Immunologically Active Heptamannoside of Mycobacterium tuberculosis by the [Au]/[Ag]-Catalyzed Activation of Ethynylcyclohexyl Glycosyl Carbonate Donor
  作者：Ganesh P. Shinde、Yogesh Sutar、Niteshlal Kasdekar、Pooja Joshi、Omid Rasool、Lech Ignatowicz、Beston Hamasur、Srinivas Hotha

  DOI：10.1021/acs.orglett.4c00175

  日期：2024.3.15

  Tuberculosis (TB) is one of the most dreadful diseases, killing more than 3 million humans annually. M. tuberculosis (MTb) is the causative agent for TB and has a thick and waxy cell wall, making it an attractive target for immunological studies. In this study, a heptamannopyranoside containing 1 → 2 and 1 → 6 α-mannopyranosidic linkages has been explored for the immunological evaluations. The conjugation-ready

  结核病 (TB) 是最可怕的疾病之一，每年夺去超过 300 万人的生命。结核分枝杆菌(MTb) 是结核病的病原体，具有厚而蜡状的细胞壁，使其成为免疫学研究的有吸引力的目标。在本研究中，探索了含有 1 → 2 和 1 → 6 α-吡喃甘露糖苷键的吡喃七甘露糖苷用于免疫学评估。通过利用最近发现的乙炔基环己基糖基碳酸酯供体的[Au]/[Ag]-糖苷化的显着特征，合成了可缀合的吡喃七甘露糖苷。该聚糖与 MTb 的早期分泌蛋白 ESAT6 缀合，用于进一步表征其作为潜在的亚单位疫苗候选者的特性。
• Comparative investigations on the regioselective mannosylation of 2,3,4-triols of mannose
  作者：Piotr Cmoch、Zbigniew Pakulski

  DOI：10.1016/j.tetasy.2008.05.032

  日期：2008.6

  Regioselective glycosylation of 2,3,4-unprotected benzyl alpha-D-mannopyranoside and allyl alpha- and -beta-D-mannopyranosides has been investigated. The configuration at the anomeric centre influences the outcome of the reaction. Possible role of hydrogen-bonding network in glycosylation of the above triols used as glycosidic acceptors is discussed. (C) 2008 Elsevier Ltd. All rights reserved.
• Chemoenzymatic Synthesis of <i>Campylobacter jejuni</i> Lipo-oligosaccharide Core Domains to Examine Guillain–Barré Syndrome Serum Antibody Specificities
  作者：Tiehai Li、Margreet A. Wolfert、Na Wei、Ruth Huizinga、Bart C. Jacobs、Geert-Jan Boons

  DOI：10.1021/jacs.0c08583

  日期：2020.11.18

  Guillain-Barré syndrome is often caused by Campylobacter jejuni infection that has induced antibodies to the lipo-oligosaccharide (LOS) that cross-react with gangliosides at peripheral nerves causing polyneuropathy. To examine fine specificities of anti-ganglioside antibodies and develop a more robust platform for diagnosis and disease monitoring, we developed a chemoenzymatic approach that provided an unprecedented panel of oligosaccharides composed of the inner-core of the LOS of C. jejuni extended by various ganglioside mimics. The compounds and corresponding ganglio-oligosaccharides were printed as a microarray to examine binding specificities of lectins, anti-ganglioside antibodies, and serum antibodies of GBS patients. Although lectins and anti-ganglioside antibodies did not differentiate the ganglio-oligosaccharides and mimics, the patient serum samples bound much more strongly to the ganglioside mimics. The data indicate that antibodies have been elicited to a foreign epitope that includes a heptosyl residue unique of bacterial LOS and that these antibodies subsequently cross-react with lower affinity to gangliosides. The microarray detected anti-GM1a antibodies with high sensitivity and will be attractive for diagnosis, disease monitoring, and immunological research.