1-O-[2-O-benzoyl-3,4-di-O-benzyl-6-O-(triisopropylsilyl)-α-D-mannopyranosyl] trichloroacetimidate | 883878-61-3

• 分子结构分类: 有机化合物 - 有机氧化合物
• 英文名称: 1-O-[2-O-benzoyl-3,4-di-O-benzyl-6-O-(triisopropylsilyl)-α-D-mannopyranosyl] trichloroacetimidate
• 英文别名: [(2R,3S,4S,5R,6R)-4,5-bis(phenylmethoxy)-2-(2,2,2-trichloroethanimidoyl)oxy-6-[tri(propan-2-yl)silyloxymethyl]oxan-3-yl] benzoate
• CAS: 883878-61-3
• 化学式: C₃₈H₄₈Cl₃NO₇Si
• 分子量: 765.246
• InChiKey: MGYGIIRWLRFKQX-XIVIVISLSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  9.66
• 重原子数：
  50
• 可旋转键数：
  17
• 环数：
  4.0
• sp3杂化的碳原子比例：
  0.47
• 拓扑面积：
  96.3
• 氢给体数：
  1
• 氢受体数：
  8

反应信息

• 作为反应物：
  描述：

  1-O-[2-O-benzoyl-3,4-di-O-benzyl-6-O-(triisopropylsilyl)-α-D-mannopyranosyl] trichloroacetimidate 在 双(三甲基硫化硅) 、 三氟甲磺酸三甲基硅酯 作用下， 以 二氯甲烷 为溶剂， 反应 1.0h， 以81%的产率得到3,4-di-O-benzyl-2-O-benzoyl-6-O-tri-isopropylsilyl-1-thio-α-D-mannopyranose
  参考文献：
  名称：

  Synthesis of Glycosylthiols and Reactivity Studies

  摘要：

  The acid-catalyzed reaction of 1,2-anhydro-3,4,6-tri-O-benzyl-alpha-D-glucopyranose (7) as glycosyl donor with bis-trimethylsilyl sulfide as acceptor affords the alpha-thiol. Hence, this sterically hindered S-nucleophile as acceptor should provide with O-glycosyl trichloroacetimidates as glycosyl donors that have nonparticipating groups at C-2, glycosylthiols with the thiol group in axial position. This was confirmed for various donors (4, 16-19) with the exception of the corresponding mannosyl donor (20). However, powerful participating groups at C-2 of the donor (23-28) governed the anomeric selectivity.

  DOI：

  10.1021/jo200624e
• 作为产物：
  描述：

  1,2-O-(α-methoxybenzylidene)-3,4,6-tri-O-benzoyl-β-D-mannopyranose 在 咪唑 、 sodium methylate 、 sodium hydride 、 溶剂黄146 、 1,8-二氮杂双环[5.4.0]十一碳-7-烯 作用下， 以 四氢呋喃 、 甲醇 、 二氯甲烷 、 N,N-二甲基甲酰胺 为溶剂， 反应 28.25h， 生成 1-O-[2-O-benzoyl-3,4-di-O-benzyl-6-O-(triisopropylsilyl)-α-D-mannopyranosyl] trichloroacetimidate
  参考文献：
  名称：

  Synthesis of a Core Arabinomannan Oligosaccharide of Mycobacterium tuberculosis

  摘要：

  The synthesis of a core arabinomannan (AM) oligosaccharide from Mycobacterium tuberculosis has been achieved using a convergent [6 + 6] glycosylation strategy and a defined set of building blocks. Dodecasaccharide 1, containing the key AM structural features of lipoarabinomannan (LAM), was obtained in excellent yield and selectivity from hexamannan 3 and hexaarabinan 5. This flexible synthetic strategy involves late-stage couplings and modifications, thus providing ready access to several different LAM fragments. The incorporation of a thiol linker at the reducing end of the oligosaccharide allows for the attachment of these compounds to microarrays and protein carriers.

  DOI：

  10.1021/jo061233x

文献信息

• Total Synthesis of Phosphatidylinositol Mannosides of <i>Mycobacterium tuberculosis</i>
  作者：Xinyu Liu、Bridget L. Stocker、Peter H. Seeberger

  DOI：10.1021/ja0565368

  日期：2006.3.1

  The total synthesis of phosphatidylinositol mannosides (PIMs), a key class of antigenic glycolipids found on the cell wall of Mycobacterium tuberculosis, is described. The synthetic strategy relied on a [4 + 3] glycosylation of tetramannoside 1 and pseudotrisaccharide 2, which allowed for convergent access to the glycan backbone of the phosphatidylinositol dimannoside (PIM2) and hexamannoside (PIM6)

  描述了磷脂酰肌醇甘露糖苷 (PIM) 的全合成，这是在结核分枝杆菌细胞壁上发现的一类关键抗原糖脂。合成策略依赖于四甘露糖苷 1 和假三糖 2 的 [4 + 3] 糖基化，这允许聚合访问磷脂酰肌醇二甘露糖苷 (PIM2) 和六甘露糖苷 (PIM6) 的聚糖骨架。基于铜催化的交叉偶联反应实现了结核硬脂酸的简短实用合成。聚糖和脂质部分的结合导致了天然 PIM2 和 PIM6 的首次全合成。
• Synthesis and immunogenicity of the <i>Mycobacterium tuberculosis</i> arabinomannan–CRM197 conjugate
  作者：Yunsong Chang、Xin Meng、Yaxin Li、Jianmei Liang、Tingshen Li、Demei Meng、Tao Zhu、Peng Yu

  DOI：10.1039/c8md00546j

  日期：——

  T-dependent conjugate vaccine. Preliminary mice immunization studies on the neoglycoconjugate revealed that it could give rise to a strong IgG antibody titer in mice at 4.0 μg dose with an aluminum phosphate adjuvant. AM–CRM197 shows potential as an excellent candidate for a new carbohydrate-based vaccine that would be capable of eliciting a protective immune response against tuberculosis.

  Lipoarabinomannan（LAM）是结核分枝杆菌的主要结构表面成分。这项研究描述了明确定义的脂阿拉伯糖甘露聚糖（LAM）特异性十二糖-蛋白质结合物的合成和免疫学研究。阿拉伯甘露聚糖（AM）十二糖已被有效地合成并与载体蛋白共价缀合，包括交叉反应突变体（CRM197）白喉类毒素和牛血清白蛋白（BSA）用于新型新糖缀合物，从而产生了强效的T依赖性缀合物疫苗。小鼠对新糖缀合物的初步免疫研究表明，使用磷酸铝佐剂可以以4.0μg的剂量在小鼠中产生较强的IgG抗体效价。AM-CRM197有望成为新型碳水化合物疫苗的潜在候选者，该疫苗能够引发针对肺结核的保护性免疫应答。
• Synthesis of a Core Arabinomannan Oligosaccharide of <i>Mycobacterium tuberculosis</i>
  作者：Alexandra Hölemann、Bridget L. Stocker、Peter H. Seeberger

  DOI：10.1021/jo061233x

  日期：2006.10.1

  The synthesis of a core arabinomannan (AM) oligosaccharide from Mycobacterium tuberculosis has been achieved using a convergent [6 + 6] glycosylation strategy and a defined set of building blocks. Dodecasaccharide 1, containing the key AM structural features of lipoarabinomannan (LAM), was obtained in excellent yield and selectivity from hexamannan 3 and hexaarabinan 5. This flexible synthetic strategy involves late-stage couplings and modifications, thus providing ready access to several different LAM fragments. The incorporation of a thiol linker at the reducing end of the oligosaccharide allows for the attachment of these compounds to microarrays and protein carriers.
• Synthesis of Glycosylthiols and Reactivity Studies
  作者：Ravindra T. Dere、Amit Kumar、Vipin Kumar、Xiangming Zhu、Richard R. Schmidt

  DOI：10.1021/jo200624e

  日期：2011.9.16

  The acid-catalyzed reaction of 1,2-anhydro-3,4,6-tri-O-benzyl-alpha-D-glucopyranose (7) as glycosyl donor with bis-trimethylsilyl sulfide as acceptor affords the alpha-thiol. Hence, this sterically hindered S-nucleophile as acceptor should provide with O-glycosyl trichloroacetimidates as glycosyl donors that have nonparticipating groups at C-2, glycosylthiols with the thiol group in axial position. This was confirmed for various donors (4, 16-19) with the exception of the corresponding mannosyl donor (20). However, powerful participating groups at C-2 of the donor (23-28) governed the anomeric selectivity.