利用光延反应便捷制备3,5-脱水和2,5-脱水戊呋喃糖苷以及5,6-脱水-D-葡萄糖呋喃糖。

Convenient preparation of 3,5-anhydro- and 2,5-anhydropentofuranosides, and 5,6-anhydro-D-glucofuranose by use of the Mitsunobu reaction.

作者信息

Schulze Oliver, Voss Jürgen, Adiwidjaja Gunadi

机构信息

Institut für Organische Chemie der Universität Hamburg, Martin-Luther-King-Platz 6, D-20146 Hamburg, Germany.

出版信息

Carbohydr Res. 2005 Mar 21;340(4):587-95. doi: 10.1016/j.carres.2004.12.027.

DOI:10.1016/j.carres.2004.12.027

PMID:15721328

Abstract

Methyl 3,5-anhydro-alpha-D-xylofuranosides are obtained by use of the Mitsunobu reaction from 2-O-protected methyl alpha-D-xylofuranosides, which are easily prepared from D-xylose. The Mitsunobu reaction of methyl 3-N-benzylamino-3-deoxy- and 3-azido-3-deoxyarabinofuranosides, which are prepared from the conveniently available methyl 2,3-anhydro-alpha-D- and 2,3-anhydro-alpha-l-lyxofuranosides by nucleophilic ring opening, yields the corresponding methyl 2,5-anhydro-alpha-D- and 2,5-anhydro-alpha-l-arabinofuranosides. Ring opening of 3,5-anhydro-1,2-O-isopropylidene-alpha-D-xylofuranose with azide yields the corresponding 5-azido derivative. The structure and configuration of the products is confirmed by NMR spectroscopy. 5,6-Anhydro-1,2-O-isopropylidene-alpha-D-glucofuranose is formed by the Mitsunobu reaction of 1,2-O-isopropylidene-alpha-D-glucofuranose. Its structure is verified by single-crystal X-ray diffraction analysis.

摘要

3,5-脱水-α-D-木呋喃糖甲酯是通过Mitsunobu反应从2-O-保护的α-D-木呋喃糖甲酯制得的，而2-O-保护的α-D-木呋喃糖甲酯可由D-木糖轻松制备。3-N-苄基氨基-3-脱氧和3-叠氮基-3-脱氧阿拉伯呋喃糖甲酯的Mitsunobu反应，是由方便可得的2,3-脱水-α-D-和2,3-脱水-α-L-来苏呋喃糖甲酯通过亲核开环制备的，反应生成相应的2,5-脱水-α-D-和2,5-脱水-α-L-阿拉伯呋喃糖甲酯。3,5-脱水-1,2-O-异亚丙基-α-D-木呋喃糖与叠氮化物的开环反应生成相应的5-叠氮基衍生物。产物的结构和构型通过核磁共振光谱法得到证实。5,6-脱水-1,2-O-异亚丙基-α-D-葡萄糖呋喃糖是由1,2-O-异亚丙基-α-D-葡萄糖呋喃糖的Mitsunobu反应形成的。其结构通过单晶X射线衍射分析得到验证。