Methyl 4,6-di-O-benzoyl-3-O-benzyl-2-deoxy-2-C-formyl-α-D-mannopyranoside | 181506-86-5

• 分子结构分类: 有机化合物 - 有机氧化合物
• 英文名称: Methyl 4,6-di-O-benzoyl-3-O-benzyl-2-deoxy-2-C-formyl-α-D-mannopyranoside
• CAS: 181506-86-5
• 化学式: C₂₉H₂₈O₈
• 分子量: 504.537
• InChiKey: YOZRHDGPNHUGMS-GRDIGNMCSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  3.84
• 重原子数：
  37.0
• 可旋转键数：
  10.0
• 环数：
  4.0
• sp3杂化的碳原子比例：
  0.28
• 拓扑面积：
  97.36
• 氢给体数：
  0.0
• 氢受体数：
  8.0

反应信息

• 作为反应物：
  描述：

  Methyl 4,6-di-O-benzoyl-3-O-benzyl-2-deoxy-2-C-formyl-α-D-mannopyranoside 在 palladium on activated charcoal samarium diiodide 、 偶氮二异丁腈 、 五氟苯酚 、 三苯基氢化锡 、 四丁基氟化铵 、 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 44.17h， 生成 methyl 2-deoxy-2-C-(α-D-manopyranosylmethyl)-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
• 作为产物：
  描述：

  6-O-(叔丁基二苯基甲硅烷基)-D-葡萄烯糖 在 吡啶 、 N-碘代丁二酰亚胺 、 偶氮二异丁腈 、 3 A molecular sieve 、 四丁基氟化铵 、 四丁基溴化铵 、 三正丁基氢锡 、 二正丁基氧化锡 、 臭氧 、 三苯基膦 作用下， 以 四氢呋喃 、 乙腈 、 苯 为溶剂， 反应 35.42h， 生成 Methyl 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
• 作为试剂：
  描述：

  D-葡萄烯糖 、 alkaline earth salt of/the/ methylsulfuric acid 在 吡啶 、 咪唑 、 N-碘代丁二酰亚胺 、 samarium diiodide 、 ammonium cerium(IV) nitrate 、 偶氮二异丁腈 、 五氟苯酚 、 3 A molecular sieve 、 三氟化硼乙醚 、 三苯基氢化锡 、 四丁基氟化铵 、 四丁基溴化铵 、 水 、 三正丁基氢锡 、 二正丁基氧化锡 、 碳酸氢钠 、 臭氧 、 1,8-二氮杂双环[5.4.0]十一碳-7-烯 、 间氯过氧苯甲酸 、 三苯基膦 、 Methyl 4,6-di-O-benzoyl-3-O-benzyl-2-deoxy-2-C-formyl-α-D-mannopyranoside 作用下， 以 四氢呋喃 、 二氯甲烷 、 N,N-二甲基甲酰胺 、 甲苯 、 乙腈 、 苯 为溶剂， 反应 59.34h， 生成 4,6-Di-O-benzoyl-3-O-benzyl-1,2-deoxy-2-C-(2-O-tert-butyldimethylsilyl-3,4,6-tri-O-benzyl-α-D-mannopyranosyl)-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

• The stereospecific synthesis of methyl α-C-mannobioside: a potential inhibitor of M. tuberculosis binding to human macrophages
  作者：Olivier Jarreton、Troels Skrydstrup、Jean-Marie Beau

  DOI：10.1039/cc9960001661

  日期：——

  The synthesis of the C-glycoside analogue of the mycobacteria capping disaccharide, Man alpha 1-2Man, employing a glycosyl organosamarium is described.