(1-adamantyl) 2-O-benzyl-4,6-O-benzylidene-3-deoxy-3-fluoro-β-D-mannopyranoside

• 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: (1-adamantyl) 2-O-benzyl-4,6-O-benzylidene-3-deoxy-3-fluoro-β-D-mannopyranoside
• 英文别名: (2R,4aR,6S,7R,8S,8aR)-6-(1-adamantyloxy)-8-fluoro-2-phenyl-7-phenylmethoxy-4,4a,6,7,8,8a-hexahydropyrano[3,2-d][1,3]dioxine
• 化学式: C₃₀H₃₅FO₅
• 分子量: 494.603
• InChiKey: IBGOQJSFAGGOEL-PGEHXPAUSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  5.6
• 重原子数：
  36
• 可旋转键数：
  6
• 环数：
  8.0
• sp3杂化的碳原子比例：
  0.6
• 拓扑面积：
  46.2
• 氢给体数：
  0
• 氢受体数：
  6

反应信息

• 作为产物：
  描述：

  phenyl 2,4,6-tri-O-acetyl-3-deoxy-3-fluoro-1-thio-β-D-glucopyranoside 在 三氟甲磺酸酐 4 A molecular sieve 、 camphor-10-sulfonic acid 、 sodium methylate 、 L-Selectride 、 sodium hydride 、 戴斯-马丁氧化剂 、 sulfobromophthalein sodium 作用下， 以 四氢呋喃 、 甲醇 、 二氯甲烷 、 N,N-二甲基甲酰胺 为溶剂， 反应 16.83h， 生成 (1-adamantyl) 2-O-benzyl-4,6-O-benzylidene-3-deoxy-3-fluoro-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

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.