phenyl 3-O-allyl-2-O-benzyl-4,6-O-(p-methoxybenzylidene)-α-D-thiomannopyranoside | 902751-14-8

• 分子结构分类: 有机化合物 - 有机氧化合物
• 英文名称: phenyl 3-O-allyl-2-O-benzyl-4,6-O-(p-methoxybenzylidene)-α-D-thiomannopyranoside
• CAS: 902751-14-8
• 化学式: C₃₀H₃₂O₆S
• 分子量: 520.646
• InChiKey: NZYNJIWXNSDIGV-RTJSNJMCSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  5.78
• 重原子数：
  37.0
• 可旋转键数：
  10.0
• 环数：
  5.0
• sp3杂化的碳原子比例：
  0.33
• 拓扑面积：
  55.38
• 氢给体数：
  0.0
• 氢受体数：
  7.0

反应信息

• 作为反应物：
  描述：

  phenyl 3-O-allyl-2-O-benzyl-4,6-O-(p-methoxybenzylidene)-α-D-thiomannopyranoside 在 草酰氯 、 camphor-10-sulfonic acid 、 二异丁基氢化铝 、 二甲基亚砜 作用下， 以 二氯甲烷 、 甲苯 为溶剂， 反应 19.0h， 生成 phenyl 3-O-allyl-2,7-di-O-benzyl-4,6-O-benzylidene-D-glycero-α-D-thio-manno-heptopyranoside
  参考文献：
  名称：

  Stereocontrolled Synthesis of the d- and l-glycero-β-d-manno-Heptopyranosides and Their 6-Deoxy Analogues. Synthesis of Methyl α-l-Rhamno-pyranosyl-(1→3)-d-glycero-β-d-manno-heptopyranosyl- (1→3)-6-deoxy-glycero-β-d-manno-heptopyranosyl-(1→4)-α-l- rhamno-pyranoside, a Tetrasaccharide Subunit of the Lipopolysaccharide from Plesimonas shigelloides

  摘要：

  The synthesis of D-and L-glycero-alpha-manno-thioheptopyranosides, protected with 4,6-O-alkylidenetype acetals is described. In glycosylations carried out with preactivation with the 1-benzenesulfinylpiperidine/trifluoromethanesulfonic anhydride couple, both the D-and L-glycero series exhibit excellent, beta-selectivity with a range of glycosyl acceptors. In contrast, a 4,7-O-alkylidene acetal was found not to afford, beta-selectivity. With a 4,6-O-[1-cyano-2-(2-iodophenyl) ethylidene] acetal protected thioglycoside, excellent, beta-selectivity was obtained in glycosylation reactions, and subsequent treatment with tributyltin hydride and azoisobutyronitrile brought about clean fragmentation to the 6-deoxy-glycero-beta-D-manno-heptopyranosides. This chemistry was applied to the stereocontrolled synthesis of methyl alpha-L-rhamno-pyranosyl-(1 -> 3)-D-glycero-beta- D-manno-heptopyranosyl-(1 -> 3)-6-deoxy-glycero-beta-D-manno-heptopyranosyl-(1 -> 4)-alpha-L-rhamno-pyranoside, a component of the lipopolysaccharide from Plesimonas shigelloides.

  DOI：

  10.1021/ja061594u
• 作为产物：
  描述：

  溴甲苯 、 3-溴丙烯 、 phenyl 4,6-O-p-methoxybenzylidene-1-thio-α-D-mannopyranoside 在 二正丁基氧化锡 、 cesium fluoride 、 sodium hydride 作用下， 以 甲苯 、 N,N-二甲基甲酰胺 、 四氢呋喃 为溶剂， 反应 17.0h， 以74%的产率得到phenyl 3-O-allyl-2-O-benzyl-4,6-O-(p-methoxybenzylidene)-α-D-thiomannopyranoside
  参考文献：
  名称：

  Stereocontrolled Synthesis of the d- and l-glycero-β-d-manno-Heptopyranosides and Their 6-Deoxy Analogues. Synthesis of Methyl α-l-Rhamno-pyranosyl-(1→3)-d-glycero-β-d-manno-heptopyranosyl- (1→3)-6-deoxy-glycero-β-d-manno-heptopyranosyl-(1→4)-α-l- rhamno-pyranoside, a Tetrasaccharide Subunit of the Lipopolysaccharide from Plesimonas shigelloides

  摘要：

  The synthesis of D-and L-glycero-alpha-manno-thioheptopyranosides, protected with 4,6-O-alkylidenetype acetals is described. In glycosylations carried out with preactivation with the 1-benzenesulfinylpiperidine/trifluoromethanesulfonic anhydride couple, both the D-and L-glycero series exhibit excellent, beta-selectivity with a range of glycosyl acceptors. In contrast, a 4,7-O-alkylidene acetal was found not to afford, beta-selectivity. With a 4,6-O-[1-cyano-2-(2-iodophenyl) ethylidene] acetal protected thioglycoside, excellent, beta-selectivity was obtained in glycosylation reactions, and subsequent treatment with tributyltin hydride and azoisobutyronitrile brought about clean fragmentation to the 6-deoxy-glycero-beta-D-manno-heptopyranosides. This chemistry was applied to the stereocontrolled synthesis of methyl alpha-L-rhamno-pyranosyl-(1 -> 3)-D-glycero-beta- D-manno-heptopyranosyl-(1 -> 3)-6-deoxy-glycero-beta-D-manno-heptopyranosyl-(1 -> 4)-alpha-L-rhamno-pyranoside, a component of the lipopolysaccharide from Plesimonas shigelloides.

  DOI：

  10.1021/ja061594u