methyl 5-O-benzoyl-2-deoxy-2-t-butylthio-β-D-xylofuranosyl-(1->6)-2,3,4-tri-O-benzoyl-α-D-mannopyranoside | 1187662-82-3

• 分子结构分类: 有机化合物 - 有机酸及其衍生物 - 羧酸及其衍生物
• 英文名称: methyl 5-O-benzoyl-2-deoxy-2-t-butylthio-β-D-xylofuranosyl-(1->6)-2,3,4-tri-O-benzoyl-α-D-mannopyranoside
• 英文别名: tBuS(-2d)[Bz(-5)]Xylf(b1-6)[Bz(-2)][Bz(-3)][Bz(-4)]a-Man1Me；[(2R,3S,4R,5R)-4-tert-butylsulfanyl-3-hydroxy-5-[[(2R,3R,4S,5S,6S)-3,4,5-tribenzoyloxy-6-methoxyoxan-2-yl]methoxy]oxolan-2-yl]methyl benzoate
• CAS: 1187662-82-3
• 化学式: C₄₄H₄₆O₁₃S
• 分子量: 814.907
• InChiKey: UJMHEAVIIQFCRB-ITTHFTHESA-N

计算性质

• 辛醇/水分配系数(LogP)：
  7.1
• 重原子数：
  58
• 可旋转键数：
  19
• 环数：
  6.0
• sp3杂化的碳原子比例：
  0.36
• 拓扑面积：
  188
• 氢给体数：
  1
• 氢受体数：
  14

反应信息

• 作为产物：
  描述：

  methyl 2,3,4-tri-O-benzoyl-α-D-mannopyranoside 、 t-butyl 2,3-anhydro-5-O-benzoyl-1-thio-α-D-lyxofuranoside 在 copper(II) bis(trifluoromethanesulfonate) 作用下， 以 二氯甲烷 为溶剂， 反应 2.5h， 以77%的产率得到methyl 5-O-benzoyl-2-deoxy-2-t-butylthio-β-D-xylofuranosyl-(1->6)-2,3,4-tri-O-benzoyl-α-D-mannopyranoside
  参考文献：
  名称：

  2,3-Anhydrosugars in Glycoside Bond Synthesis: Mechanism of 2-Deoxy-2-thioaryl Glycoside Formation

  摘要：

  A series of investigations probing the mechanism of the 2,3-anhydrosugar migration-glycosylation reaction were performed using a thioglycoside with the D-lyxo stereochemistry as the substrate. Among the work reported are the results of quantum mechanical calculations, NMR studies, the measurement of a-deuterium kinetic isotope effects, and the synthesis of a series of substrate analogues. All studies point to a consistent finding: that the reaction proceeds through an oxocarbenium ion intermediate, not an episulfonium ion as previously suggested. It is proposed that the high stereoselectivity of the reaction arises from a preferred "inside attack" of the nucleophile onto the oxocarbenium ion intermediate.

  DOI：

  10.1021/ja9029945

文献信息

• 2,3-Anhydrosugars in Glycoside Bond Synthesis: Mechanism of 2-Deoxy-2-thioaryl Glycoside Formation
  作者：Dianjie Hou、Hashem A. Taha、Todd L. Lowary

  DOI：10.1021/ja9029945

  日期：2009.9.16

  A series of investigations probing the mechanism of the 2,3-anhydrosugar migration-glycosylation reaction were performed using a thioglycoside with the D-lyxo stereochemistry as the substrate. Among the work reported are the results of quantum mechanical calculations, NMR studies, the measurement of a-deuterium kinetic isotope effects, and the synthesis of a series of substrate analogues. All studies point to a consistent finding: that the reaction proceeds through an oxocarbenium ion intermediate, not an episulfonium ion as previously suggested. It is proposed that the high stereoselectivity of the reaction arises from a preferred "inside attack" of the nucleophile onto the oxocarbenium ion intermediate.