α-D-Mannosyl 2-pyridyl sulfone | 188893-00-7

• 分子结构分类: 有机化合物 - 有机氧化合物
• 英文名称: α-D-Mannosyl 2-pyridyl sulfone
• 英文别名: 2,3,4,6-tetra-O-benzyl-α-D-mannopyranosyl 2'-pyridyl sulfone；2-(((2R,3S,4S,5R,6R)-3,4,5-tris(benzyloxy)-6-((benzyloxy)methyl)tetrahydro-2H-pyran-2-yl)sulfonyl)pyridine；2-[(2R,3S,4S,5R,6R)-3,4,5-tris(phenylmethoxy)-6-(phenylmethoxymethyl)oxan-2-yl]sulfonylpyridine
• CAS: 188893-00-7
• 化学式: C₃₉H₃₉NO₇S
• 分子量: 665.807
• InChiKey: MGKNLYNEULNGFT-JXMWNMMWSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  5.9
• 重原子数：
  48
• 可旋转键数：
  15
• 环数：
  6.0
• sp3杂化的碳原子比例：
  0.26
• 拓扑面积：
  102
• 氢给体数：
  0
• 氢受体数：
  8

反应信息

• 作为反应物：
  描述：

  α-D-Mannosyl 2-pyridyl sulfone 在 palladium on activated charcoal 、 samarium diiodide 、 偶氮二异丁腈 、 五氟苯酚 、 三苯基氢化锡 、 氢气 、 sodium methylate 、 溶剂黄146 作用下， 以 四氢呋喃 、 甲醇 、 甲苯 、 乙腈 为溶剂， 反应 0.5h， 生成 methyl 3-deoxy-3-C-[(α-D-mannopyranosyl)methyl]-α-D-mannopyranoside
  参考文献：
  名称：

  Application of the Anomeric Samarium Route for the Convergent Synthesis of the C-Linked Trisaccharide α-d-Man-(1→3)-[α-d-Man-(1→6)]-d-Man and the Disaccharides α-d-Man-(1→3)-d-Man and α-d-Man-(1→6)-d-Man

  摘要：

  Studies are reported on the assembly of the branched C-trisaccharide, alpha-D-Man-(1-->3)-[alpha-D-Man-(1-->6)]-D-Man, representing the core region of the asparagine-linked oligosaccharides. The key step in this synthesis uses a SmI2-mediated coupling of two mannosylpyridyl sulfones to a C3,C6-diformyl branched monosaccharide unit, thereby assembling all three sugar units in one reaction and with complete stereocontrol at the two anomeric carbon centers. Subsequent tin hydride-based deoxygenation followed by a deprotection step produces the target C-trimer. In contrast to many of the other C-glycosylation methods, this approach employes intact carbohydrate units as C-glycosyl donors and acceptors, which in many instances parallels the well-studied O-glycosylation reactions. The synthesis of the C-disaccharides alpha-D-Man-(1-->3)-D-Man and alpha-D-Man-(1-->6)-D-Man is also described, they being necessary for the following conformational studies of all three carbohydrate analogues both in solution and bound to several mannose-binding proteins.

  DOI：

  10.1021/jo020339z
• 作为产物：
  描述：

  2,3,4,6-tetra-O-benzyl-α-D-mannopyranosyl trichloroacetimidate 在 三氟化硼乙醚 、 碳酸氢钠 、 间氯过氧苯甲酸 作用下， 以 二氯甲烷 为溶剂， 反应 3.5h， 生成 α-D-Mannosyl 2-pyridyl sulfone
  参考文献：
  名称：

  A General Approach to 1,2-trans-C-Glycosides via Glycosyl Samarium(III) Compounds

  摘要：

  DOI：

  10.1002/(sici)1521-3765(19980416)4:4<655::aid-chem655>3.3.co;2-w

文献信息

• Synthesis of α-C-Glycosides by Samarium Diiodide Mediated Coupling of Glycosyl Pyridyl Sulfones with Alkenes
  作者：Xin-Shan Ye、Gen Li、De-Cai Xiong

  DOI：10.1055/s-0030-1261230

  日期：2011.10

  A mild method for the synthesis of α-C-glycosides by the samarium diiodide mediated coupling reactions of glycosyl 2-pyridyl sulfones with different α,β-unsaturated carbonyl compounds has been developed. This method allows the use of less amount of substrates. C-glycosides - samarium diiodide - glycosyl 2-pyridyl sulfones - coupling reaction

  已经开发了一种温和的方法，该方法通过二碘化sa介导的糖基2-吡啶基砜与不同的α，β-不饱和羰基化合物的偶联反应合成α- C-糖苷。该方法允许使用较少量的基板。 C-糖苷-二碘化mar-糖基2-吡啶基砜-偶联反应
• A convergent synthesis of α-C-1,3-mannobioside via SmI2-promoted C-glycosylation
  作者：Sussie L Krintel、Jesús Jiménez-Barbero、Troels Skrydstrup

  DOI：10.1016/s0040-4039(99)01604-4

  日期：1999.10

  The C-disaccharide of α-1,3-mannobioside has been synthesized via the direct coupling of a mannosyl pyridyl sulfone and a C-formyl branched sugar with the one electron reducing agent, SmI2. The sterically hindered alcohol obtained in this coupling was successfully removed employing our previously described deoxygenating conditions.

  所述Ç α-1,3-mannobioside的-disaccharide合成了通过甘露糖吡啶基砜和直接耦合Ç甲酰基支链与所述一个电子还原剂，SMI糖2。使用我们先前描述的脱氧条件，成功除去了在该偶联反应中获得的位阻醇。
• A highly convergent synthesis of a branched C-trisaccharide employing a double SmI2-promoted C-glycosylation
  作者：Lise Munch Mikkelsen、Sussie Lerche Krintel、Troels Skrydstrup、Jesús Jiménez-Barbero

  DOI：10.1039/b007117j

  日期：——

  The branched C-trisaccharide analogue of α-D-Man-(1→3)-[α-D-Man-(1→6)]- D-Man has been synthesised by the SmI2-mediated coupling of two mannosyl pyridyl sulfone units to a monosaccharide dialdehyde. This approach represents a highly convergent synthesis of a C-oligosaccharide.

  通过 SmI2- 介导的两个甘露糖基吡啶砜单元与单糖二醛的偶联，合成了 α-D-Man-(1→3)-[α-D-Man-(1→6)]- D-Man 的支链 C 三糖类似物。这种方法代表了一种 C-寡糖的高度聚合合成。
• Radical dimerization of glycosyl 2-pyridylsulfones with samarium (II) iodide in the presence of HMPA
  作者：Gilles Doisneau、Jean-Marie Beau

  DOI：10.1016/s0040-4039(98)00568-1

  日期：1998.5

  Reduction of glycosyl 2-pyridylsulfones by samarium (II) iodide in the presence of HMPA leads to glycosyl dimers in up to 74% yield. This is rationalized by a free-radical mechanism.

  在HMPA存在下，通过碘化sa（II）还原糖基2-吡啶基砜可导致糖基二聚体的产率高达74％。这是通过自由基机制合理化的。
• Further studies in α-C-mannosylation promoted by samarium diiodide
  作者：Olivier Jarreton、Troels Skrydstrup、Jean-Marie Beau

  DOI：10.1016/s0040-4039(97)00206-2

  日期：1997.3

  Mannosyl pyridylsulfones with varying C2OH protecting groups were reacted with cyclohexanone in the presence of SmI2. With SiMe2tBu and Bn, high yields of an α-C-mannoside were obtained. In the former case no β-elimination was observed. The relative configuration of the major diastereomer obtained upon coupling with aldehydes was determined.

  在SmI 2的存在下，具有不同C2 = OH保护基的甘露糖基吡啶基砜与环己酮反应。使用SiMe 2 t Bu和Bn，可获得高收率的α - C-甘露糖苷。在前一种情况下，未观察到β-消除。确定了与醛偶联后获得的主要非对映异构体的相对构型。