一种将伯醇氧化为羧酸的简便方法及其在糖胺聚糖合成中的应用。
A facile method for oxidation of primary alcohols to carboxylic acids and its application in glycosaminoglycan syntheses.
作者信息
Huang Lijun, Teumelsan Nardos, Huang Xuefei
机构信息
Department of Chemistry, The University of Toledo, 2801 W. Bancroft St. MS 602, Toledo, OH 43606, USA.
出版信息
Chemistry. 2006 Jul 5;12(20):5246-52. doi: 10.1002/chem.200600290.
Abstract
A convenient two-step, one-pot procedure was developed for the conversion of primary alcohols to carboxylic acids. The alcohol was first treated with NaOCl and TEMPO under phase-transfer conditions, followed by NaClO2 oxidation in one pot. This reaction is applicable to a wide range of alcohols and the mild reaction conditions are compatible with many sensitive functional groups, including electron-rich aromatic rings, acid-labile isopropylidene ketal and glycosidic linkages, and oxidation-prone thioacetal, p-methoxybenzyl, and allyl moieties. Several glycosaminoglycans such as heparin, chondroitin, and hyaluronic acid oligosaccharides have been synthesized in high yields by using this new oxidation protocol.
摘要
开发了一种便捷的两步一锅法，用于将伯醇转化为羧酸。首先在相转移条件下用次氯酸钠（NaOCl）和2,2,6,6-四甲基哌啶-1-氧化物（TEMPO）处理醇，然后在同一反应容器中进行亚氯酸钠（NaClO₂）氧化。该反应适用于多种醇，温和的反应条件与许多敏感官能团兼容，包括富电子芳环、对酸不稳定的异亚丙基缩酮和糖苷键，以及易氧化的硫代乙缩醛、对甲氧基苄基和烯丙基部分。通过使用这种新的氧化方法，已高产率地合成了几种糖胺聚糖，如肝素、软骨素和透明质酸寡糖。
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