benzoxazol-2-yl 2,3,4-tri-O-benzoyl-6-O-(2,3,4,6-tetra-O-benzoyl-β-D-glucopyranosyl)-1-thio-β-D-glucopyranoside | 1117896-25-9

• 分子结构分类: 有机化合物 - 有机氧化合物
• 英文名称: benzoxazol-2-yl 2,3,4-tri-O-benzoyl-6-O-(2,3,4,6-tetra-O-benzoyl-β-D-glucopyranosyl)-1-thio-β-D-glucopyranoside
• 英文别名: 2-benzoxazolyl 2,3,4-tri-O-benzoyl-6-O-(2,3,4,6-tetra-O-benzoyl-β-D-glucopyranosyl)-1-thio-β-D-glucopyranoside；[(2R,3R,4S,5R,6R)-6-[[(2R,3R,4S,5R,6S)-6-(1,3-benzoxazol-2-ylsulfanyl)-3,4,5-tribenzoyloxyoxan-2-yl]methoxy]-3,4,5-tribenzoyloxyoxan-2-yl]methyl benzoate
• CAS: 1117896-25-9
• 化学式: C₆₈H₅₃NO₁₈S
• 分子量: 1204.23
• InChiKey: XSQIQBHPUQAJQO-YPULBFFPSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  13.4
• 重原子数：
  88
• 可旋转键数：
  27
• 环数：
  11.0
• sp3杂化的碳原子比例：
  0.18
• 拓扑面积：
  263
• 氢给体数：
  0
• 氢受体数：
  20

反应信息

• 作为反应物：
  描述：

  benzoxazol-2-yl 2,3,4-tri-O-benzoyl-6-O-(2,3,4,6-tetra-O-benzoyl-β-D-glucopyranosyl)-1-thio-β-D-glucopyranoside 、 4,5-dihydrothiazol-2-yl 2,3,4-tri-O-benzoyl-1-thio-β-D-glucopyranoside 在 silver tetrafluoroborate 作用下， 以 1,2-二氯乙烷 为溶剂， 反应 0.67h， 以81%的产率得到methyl (2,3,4,6-tetra-O-benzoyl-β-D-glucopyranosyl)-(1->6)-(2,3,4-tri-O-benzoyl-β-D-glucopyranosyl)-(1->6)-2,3,4-tri-O-benzyl-α-D-glucopyranoside
  参考文献：
  名称：

  Unexpected Orthogonality of S-Benzoxazolyl and S-Thiazolinyl Glycosides: Application to Expeditious Oligosaccharide Assembly

  摘要：

  Thorough mechanistic studies of the alkylation pathway for the activation of glycosyl thioimidates have led to the development of the "thioimidate-only orthogonal strategy". Discrimination among S-thiazolinyl (STaz) and S-benzoxazolyl (SBox) anomeric leaving groups was achieved by fine-tuning of the activation conditions. Preferential glycosidation of a certain thioimidate is not simply determined by the strength of activating reagents; instead, the type of activation-direct vs indirect-comes to the fore and plays the key role.

  DOI：

  10.1021/ol802740b
• 作为产物：
  描述：

  benzoxazol-2-yl 2,3,4,6-tetra-O-benzoyl-1-thio-β-D-glucopyranoside 、 4,5-dihydrothiazol-2-yl 2,3,4-tri-O-benzoyl-1-thio-β-D-glucopyranoside 在 bismuth(lll) trifluoromethanesulfonate 作用下， 以 1,2-二氯乙烷 为溶剂， 反应 24.0h， 以69%的产率得到benzoxazol-2-yl 2,3,4-tri-O-benzoyl-6-O-(2,3,4,6-tetra-O-benzoyl-β-D-glucopyranosyl)-1-thio-β-D-glucopyranoside
  参考文献：
  名称：

  Unexpected Orthogonality of S-Benzoxazolyl and S-Thiazolinyl Glycosides: Application to Expeditious Oligosaccharide Assembly

  摘要：

  Thorough mechanistic studies of the alkylation pathway for the activation of glycosyl thioimidates have led to the development of the "thioimidate-only orthogonal strategy". Discrimination among S-thiazolinyl (STaz) and S-benzoxazolyl (SBox) anomeric leaving groups was achieved by fine-tuning of the activation conditions. Preferential glycosidation of a certain thioimidate is not simply determined by the strength of activating reagents; instead, the type of activation-direct vs indirect-comes to the fore and plays the key role.

  DOI：

  10.1021/ol802740b

文献信息

• On Orthogonal and Selective Activation of Glycosyl Thioimidates and Thioglycosides: Application to Oligosaccharide Assembly
  作者：Sophon Kaeothip、Alexei V. Demchenko

  DOI：10.1021/jo201117s

  日期：2011.9.16

  Discrimination among S-thiazolinyl (STaz), S-benzoxazolyl (SBox), and S-ethyl anomeric leaving groups was achieved by fine-tuning activation conditions. Preferential glycosidation of a certain leaving group is determined neither by the strength of the activating reagent nor by the stability of the leaving group itself; instead, the type of activation plays the key role. The activation conditions established herein were applied to a sequential five-step synthesis of a hexasaccharide using six monosaccharide building blocks equipped with six different leaving groups.