p-Methoxyphenylmethyl 4,6-di-O-benzoyl-3-O-benzyl-2-deoxy-2-C-formyl-α-D-mannopyranoside | 188893-05-2

• 分子结构分类: 有机化合物 - 有机氧化合物
• 英文名称: p-Methoxyphenylmethyl 4,6-di-O-benzoyl-3-O-benzyl-2-deoxy-2-C-formyl-α-D-mannopyranoside
• 英文别名: [(2R,3S,4R,5R,6S)-3-benzoyloxy-5-formyl-6-[(4-methoxyphenyl)methoxy]-4-phenylmethoxyoxan-2-yl]methyl benzoate
• CAS: 188893-05-2
• 化学式: C₃₆H₃₄O₉
• 分子量: 610.661
• InChiKey: CEBXTXHKRUIWIA-IAZPGZMQSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  5.4
• 重原子数：
  45
• 可旋转键数：
  15
• 环数：
  5.0
• sp3杂化的碳原子比例：
  0.25
• 拓扑面积：
  107
• 氢给体数：
  0
• 氢受体数：
  9

反应信息

• 作为反应物：
  描述：

  p-Methoxyphenylmethyl 4,6-di-O-benzoyl-3-O-benzyl-2-deoxy-2-C-formyl-α-D-mannopyranoside 在 sodium tetrahydroborate 、 ammonium cerium(IV) nitrate 、 水 作用下， 以 乙腈 为溶剂， 生成 ((2R,3S,4R,5S,6S)-3-(benzoyloxy)-4-(benzyloxy)-5-(((tert-butyldiphenylsilyl)oxy)methyl)-6-hydroxytetrahydro-2H-pyran-2-yl)methyl benzoate
  参考文献：
  名称：

  Samarium Diiodide PromotedC-Glycosylation: An Application to the Stereospecific Synthesis ofα-1,2-C-Mannobioside and Its Derivatives

  摘要：

  The synthesis of the C-glycoside analogue of the disaccharide Man(alpha 1-->2)Man has been achieved in a highly stereoselective and efficient manner employing an approach which closely parallels O-glycoside synthesis. The key step included the samarium diiodide reduction of mannosyl pyridylsulfone 18 in the presence of the C2-formyl branched mannoside derivative 17a to furnish the C-disaccharide derivative 19a in high yield. An intramolecular formyl group transfer reaction by means of 5-exo radical cyclization and concomitant fragmentation yielded aldehyde 17a stereospecifically. We also present a potentially viable alternative for the deoxygenation of sterically encumbered secondary alcohols. Attempts to extend this procedure to the synthesis of the C-trisaccharide of Man(alpha 1-->2)Man(alpha 1-->2)Man were frustrated by the inability of the disaccharide, pyridylsulfone derivative 43, to undergo coupling with carbonyl substrates upon treatment with SmI2, possibly owing to the sterically bulky C2 substituent.

  DOI：

  10.1002/(sici)1521-3765(19990201)5:2<430::aid-chem430>3.0.co;2-d
• 作为产物：
  描述：

  4,6-Di-O-benzoyl-3-O-(1,3-diphenylprop-2-en-1-yl)-D-glucal 在 N-碘代丁二酰亚胺 、 偶氮二异丁腈 、 3 A molecular sieve 、 三正丁基氢锡 、 臭氧 、 三苯基膦 作用下， 以 乙腈 、 苯 为溶剂， 反应 4.17h， 生成 p-Methoxyphenylmethyl 4,6-di-O-benzoyl-3-O-benzyl-2-deoxy-2-C-formyl-α-D-mannopyranoside
  参考文献：
  名称：

  Samarium Diiodide PromotedC-Glycosylation: An Application to the Stereospecific Synthesis ofα-1,2-C-Mannobioside and Its Derivatives

  摘要：

  The synthesis of the C-glycoside analogue of the disaccharide Man(alpha 1-->2)Man has been achieved in a highly stereoselective and efficient manner employing an approach which closely parallels O-glycoside synthesis. The key step included the samarium diiodide reduction of mannosyl pyridylsulfone 18 in the presence of the C2-formyl branched mannoside derivative 17a to furnish the C-disaccharide derivative 19a in high yield. An intramolecular formyl group transfer reaction by means of 5-exo radical cyclization and concomitant fragmentation yielded aldehyde 17a stereospecifically. We also present a potentially viable alternative for the deoxygenation of sterically encumbered secondary alcohols. Attempts to extend this procedure to the synthesis of the C-trisaccharide of Man(alpha 1-->2)Man(alpha 1-->2)Man were frustrated by the inability of the disaccharide, pyridylsulfone derivative 43, to undergo coupling with carbonyl substrates upon treatment with SmI2, possibly owing to the sterically bulky C2 substituent.

  DOI：

  10.1002/(sici)1521-3765(19990201)5:2<430::aid-chem430>3.0.co;2-d

文献信息

• 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。
• Samarium Diiodide PromotedC-Glycosylation: An Application to the Stereospecific Synthesis ofα-1,2-C-Mannobioside and Its Derivatives
  作者：Olivier Jarreton、Troels Skrydstrup、Juan-Félix Espinosa、Jesús Jiménez-Barbero、Jean-Marie Beau

  DOI：10.1002/(sici)1521-3765(19990201)5:2<430::aid-chem430>3.0.co;2-d

  日期：1999.2.1

  The synthesis of the C-glycoside analogue of the disaccharide Man(alpha 1-->2)Man has been achieved in a highly stereoselective and efficient manner employing an approach which closely parallels O-glycoside synthesis. The key step included the samarium diiodide reduction of mannosyl pyridylsulfone 18 in the presence of the C2-formyl branched mannoside derivative 17a to furnish the C-disaccharide derivative 19a in high yield. An intramolecular formyl group transfer reaction by means of 5-exo radical cyclization and concomitant fragmentation yielded aldehyde 17a stereospecifically. We also present a potentially viable alternative for the deoxygenation of sterically encumbered secondary alcohols. Attempts to extend this procedure to the synthesis of the C-trisaccharide of Man(alpha 1-->2)Man(alpha 1-->2)Man were frustrated by the inability of the disaccharide, pyridylsulfone derivative 43, to undergo coupling with carbonyl substrates upon treatment with SmI2, possibly owing to the sterically bulky C2 substituent.