Reductive fragmentation of carbohydrate anomeric alkoxy radicals.: Synthesis of alditols with potential utility as chiral synthons
Reductive fragmentation of carbohydrate anomeric alkoxy radicals.: Synthesis of alditols with potential utility as chiral synthons
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DOI：
10.1021/jo0156565
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发表时间：
2001-10-19
影响因子：
3.6
通讯作者：
Suárez, E
中科院分区：
文献类型：
--
作者：
Francisco, CG;León, EI;Suárez, E
合成了一系列呋喃糖和吡喃糖形式碳水化合物的硝酸端粒酯和n -邻苯二胺苷，生成相应的烷氧基自由基，并研究了还原条件下C1-C2断裂反应。该反应采用两步法将碳水化合物转化为相应的少一个碳的糖醇。利用这种方法，已经制备了具有d -赤藓糖醇、d -苏糖醇、d -木糖醇和d -阿拉伯糖醇立体化学性质的天然产物合成的有趣的四碳和五碳构建块。以1,2:5,6-二- o-异丙基- β -d -葡萄糖呋喃糖和2-乙酰氨基-3,4,6-三- o-乙酰-2-脱氧-d -葡萄糖吡喃糖为原料，分别合成了1,2- o-异丙基- β - l-糖（40）和1-乙酰氨基-2,4,5-三- o-乙酰-d -阿拉伯糖醇（50）。
A series of anomeric nitrate esters and N-phthalimido glycosides of carbohydrates in furanose and pyranose forms have been synthesized in order to generate the corresponding alkoxy radicals and study the C1-C2 fragmentation reaction under reductive conditions. This reaction constitutes a two-step method for the transformation of carbohydrates into the corresponding alditols with one less carbon. Using this methodology, interesting four- and five-carbon building blocks for natural products synthesis possessing D-erythritol, D-threitol, D-xylitol, and D-arabinitol stereochemistry have been prepared. The synthesis of 1,2-O-isopropylidene-beta -L-threose (40) and 1-acetamido-2,4,5-tri-O-acetyl-D-arabinitol (50) have also been achieved from 1,2:5,6-di-O-isopropylidene-beta -D-gluco-furanose and 2-acetamido-3,4,6-tri-O-acetyl-2-deoxy-D-glucopyranose, respectively.