methyl 4-O-(4-O-acetylferuloyl)-β-D-xylopyranoside | 137232-58-7

• 分子结构分类: 有机化合物 - 苯丙烷和聚酮 - 肉桂酸及其衍生物
• 英文名称: methyl 4-O-(4-O-acetylferuloyl)-β-D-xylopyranoside
• 英文别名: [(3R,4R,5R,6R)-4,5-dihydroxy-6-methoxyoxan-3-yl] (E)-3-(4-acetyloxy-3-methoxyphenyl)prop-2-enoate
• CAS: 137232-58-7
• 化学式: C₁₈H₂₂O₉
• 分子量: 382.367
• InChiKey: FDFLXOFNXRVVDW-QCGLBEGZSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  0.4
• 重原子数：
  27
• 可旋转键数：
  8
• 环数：
  2.0
• sp3杂化的碳原子比例：
  0.44
• 拓扑面积：
  121
• 氢给体数：
  2
• 氢受体数：
  9

反应信息

• 作为产物：
  描述：

  4-乙酰氧基-3-甲氧基肉桂酰氯 、 甲基-β-D-吡喃木糖苷 在 二正丁基氧化锡 作用下， 生成 methyl 4-O-(4-O-acetylferuloyl)-β-D-xylopyranoside 、 methyl 3,4-di-O-(4-O-acetylferuloyl)-β-D-xylopyranoside
  参考文献：
  名称：

  Regioselective protection strategies for D-xylopyranosides

  摘要：

  The acylation of D-xylopyranosides can be effected at any position by selective hydroxyl activation with dibutyltin oxide in refluxing benzene and proper choice of starting anomer. Methyl 4-O-benzyl-beta-D-xylopyranoside, available from methyl 2,3-O-isopropylidene-beta-D-xylopyranoside, provides the 2- and 3-benzoates, which are easily separable in 85% combined yield. Methyl and allyl beta-D-xylopyranosides, when treated with 1 equiv of dibutyltin and subsequently with benzoyl chloride (1 equiv), yield their corresponding 4-benzoates (80%). The use of 2 equiv of benzoyl chloride provides the 3,4-dibenzoates in excellent yield (90%). The clean conversion to mono- or dibenzoates, depending on the amount of benzoyl chloride added, suggests that the intermediate stannylene acetals provide different activation levels. A pathway involving acylation of an intermediate dibutylchlorostannyl ether is proposed to explain the observed phenomenon. This sequential selective activation is used to afford protection and differentiation of the 3- and 4-positions with a one-pot synthesis of methyl 4-O-benzoyl-3-O-(chloroacetyl)-beta-D-xylopyranoside. Methyl and benzyl alpha-D-xylopyranosides afford the 2,4-dibenzoates in good yield (> 80%) demonstrating 1,3-activation of a triol system. This protection strategy is used to prepare benzyl O-(2,3,5-tri-O-benzoyl-alpha-L-arabinofuranosyl)-(1 --> 3)-2,4-di-O-benzoyl-alpha-D-xylopyranoside from D-xylose and L-arabinose. In the final step, the silver triflate catalyzed glycosylation of benzyl 2,4-di-O-benzoyl-alpha-D-xylopyranoside by 2,3,5-tri-O-benzoyl-alpha-L-arabinofuranosyl chloride is accomplished in 91% yield.

  DOI：

  10.1021/jo00025a013