phenyl 4,6-O-benzylidene-3-deoxy-3-fluoro-1-thio-β-D-glucopyranoside | 931095-54-4

• 分子结构分类: 有机化合物 - 有机杂环化合物 - 吡喃二恶英
• 英文名称: phenyl 4,6-O-benzylidene-3-deoxy-3-fluoro-1-thio-β-D-glucopyranoside
• 英文别名: (2R,4aR,6S,7R,8R,8aR)-8-fluoro-2-phenyl-6-phenylsulfanyl-4,4a,6,7,8,8a-hexahydropyrano[3,2-d][1,3]dioxin-7-ol
• CAS: 931095-54-4
• 化学式: C₁₉H₁₉FO₄S
• 分子量: 362.422
• InChiKey: QCXQIUKBXYYEQD-UPGMHYFXSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  3.3
• 重原子数：
  25
• 可旋转键数：
  3
• 环数：
  4.0
• sp3杂化的碳原子比例：
  0.37
• 拓扑面积：
  73.2
• 氢给体数：
  1
• 氢受体数：
  6

反应信息

• 作为反应物：
  描述：

  phenyl 4,6-O-benzylidene-3-deoxy-3-fluoro-1-thio-β-D-glucopyranoside 在 L-Selectride 、 sodium hydride 、 戴斯-马丁氧化剂 作用下， 以 四氢呋喃 、 二氯甲烷 、 N,N-二甲基甲酰胺 为溶剂， 反应 8.33h， 生成 phenyl 2-O-benzyl-4,6-O-benzylidene-3-deoxy-3-fluoro-1-thio-β-D-mannopyranoside
  参考文献：
  名称：

  4,6-O-Benzylidene-Directed β-Mannopyranosylation and α-Glucopyranosylation:  The 2-Deoxy-2-fluoro and 3-Deoxy-3-fluoro Series of Donors and the Importance of the O2−C2−C3−O3 Interaction

  摘要：

  A series of 4,6-O-benzylidene-protected 2-O-benzyl-3-deoxy-3-fluoro- and 3-O-benzyl-2-deoxy-2-fluorogluco- and mannopyranosyl thioglycosides were synthesized and their coupling reactions with a series of alcohols, on preactivation with 1-benzenesulfinylpiperidine and trifluoromethanesulfonic anhydride, investigated. In all cases, the selectivities were lower than those observed with the corresponding simple 4,6-O-benzylidene 2,3-di-O-benzylgluco- and mannopyranosyl thioglycosides. This leads to the conclusion that the high beta-selectivity observed with 4,6-O-benzylidene 2,3-di-O-benzylmannopyranosyl donors under the same conditions is in large part derived from the compression of the O2-C2-C3-O3 torsion angle on going from the intermediate covalent glycosyl triflate to the oxacarbenium ion, as compared to the relaxation of this torsion angle in the gluco series.

  DOI：

  10.1021/jo062294y
• 作为产物：
  描述：

  phenyl 2,4,6-tri-O-acetyl-3-deoxy-3-fluoro-1-thio-β-D-glucopyranoside 在 camphor-10-sulfonic acid 、 sodium methylate 作用下， 以 甲醇 、 N,N-二甲基甲酰胺 为溶剂， 反应 6.0h， 生成 phenyl 4,6-O-benzylidene-3-deoxy-3-fluoro-1-thio-β-D-glucopyranoside
  参考文献：
  名称：

  4,6-O-Benzylidene-Directed β-Mannopyranosylation and α-Glucopyranosylation:  The 2-Deoxy-2-fluoro and 3-Deoxy-3-fluoro Series of Donors and the Importance of the O2−C2−C3−O3 Interaction

  摘要：

  A series of 4,6-O-benzylidene-protected 2-O-benzyl-3-deoxy-3-fluoro- and 3-O-benzyl-2-deoxy-2-fluorogluco- and mannopyranosyl thioglycosides were synthesized and their coupling reactions with a series of alcohols, on preactivation with 1-benzenesulfinylpiperidine and trifluoromethanesulfonic anhydride, investigated. In all cases, the selectivities were lower than those observed with the corresponding simple 4,6-O-benzylidene 2,3-di-O-benzylgluco- and mannopyranosyl thioglycosides. This leads to the conclusion that the high beta-selectivity observed with 4,6-O-benzylidene 2,3-di-O-benzylmannopyranosyl donors under the same conditions is in large part derived from the compression of the O2-C2-C3-O3 torsion angle on going from the intermediate covalent glycosyl triflate to the oxacarbenium ion, as compared to the relaxation of this torsion angle in the gluco series.

  DOI：

  10.1021/jo062294y

文献信息

• 4,6-<i>O</i>-Benzylidene-Directed β-Mannopyranosylation and α-Glucopyranosylation:  The 2-Deoxy-2-fluoro and 3-Deoxy-3-fluoro Series of Donors and the Importance of the O2−C2−C3−O3 Interaction
  作者：David Crich、Linfeng Li

  DOI：10.1021/jo062294y

  日期：2007.3.1

  A series of 4,6-O-benzylidene-protected 2-O-benzyl-3-deoxy-3-fluoro- and 3-O-benzyl-2-deoxy-2-fluorogluco- and mannopyranosyl thioglycosides were synthesized and their coupling reactions with a series of alcohols, on preactivation with 1-benzenesulfinylpiperidine and trifluoromethanesulfonic anhydride, investigated. In all cases, the selectivities were lower than those observed with the corresponding simple 4,6-O-benzylidene 2,3-di-O-benzylgluco- and mannopyranosyl thioglycosides. This leads to the conclusion that the high beta-selectivity observed with 4,6-O-benzylidene 2,3-di-O-benzylmannopyranosyl donors under the same conditions is in large part derived from the compression of the O2-C2-C3-O3 torsion angle on going from the intermediate covalent glycosyl triflate to the oxacarbenium ion, as compared to the relaxation of this torsion angle in the gluco series.