在无水氟化氢中通过对异构糖基果糖进行选择性质子活化合成双螺二氧杂环己烷基假低聚糖

Synthesis of dispirodioxanyl pseudo-oligosaccharides by selective protonic activation of isomeric glycosylfructoses in anhydrous hydrogen fluoride.

作者信息

Defaye J, García Fernández J M

机构信息

Département de Recherche Fondamentale, Matière Condensée/SESAM, Centre d'Etudes de Grenoble, France.

出版信息

Carbohydr Res. 1994 Jan 3;251:1-15. doi: 10.1016/0008-6215(94)84273-6.

DOI:10.1016/0008-6215(94)84273-6

PMID:8149367

Abstract

Dispirodioxanyl pseudotetrasaccharides 6-O-alpha-D-glucopyranosyl-alpha-D-fructofuranose 6-O-alpha-D-glucopyranosyl-beta-D-fructofuranose 1,2':2,1'-dianhydride, 5-O-alpha-D-glucopyranosyl-alpha-D-fructopyranose 5-O-alpha-D-glucopyranosyl-beta-D-fructopyranose 1,2':2,1'-dianhydride, 4-O-alpha-D-glucopyranosyl-alpha-D-fructofuranose 4-O-alpha-D-glucopyranosyl-beta-D-fructopyranose 1,2':2,1'-dianhydride, 4-O-beta-D-galactopyranosyl-alpha-D-fructofuranose 4-O-beta-D-galactopyranosyl-beta-D-fructopyranose 1,2':2,1'-dianhydride, and 3-O-alpha-D-glucopyranosyl-alpha-D-fructofuranose 3-O-alpha-D-glucopyranosyl-beta-D-fructofuranose 1,2':2,1'-dianhydride were respectively obtained, on a preparative scale, by dissolution of the isomeric glycosylfructoses palatinose, leucrose, maltulose, lactulose, and turanose in anhydrous hydrogen fluoride. The reaction, involving selective protonation at the free anomeric position of the fructose unit, was extended to the preparation of the pseudotrisaccharides 6-O-alpha-D-glucopyranosyl-alpha-D-fructofuranose beta-D-fructopyranose 1,2':2',1-dianhydride from palatinose and fructose, and to its 3-O-, 4-O-, and 4'-O-glucosyl analogues using turanose and maltulose as the disaccharide precursor. The cross-reactions of palatinose with maltulose and with leucrose resulted in the preparation of 6-O-alpha-D-glucopyranosyl-alpha-D-fructofuranose 4-O-alpha-D-glucopyranosyl-beta-D-fructopyranose 1,2':2,1'-dianhydride and 6-O-alpha-D-glucopyranosyl-alpha-D-fructofuranose 5-O-alpha-D-glucopyranosyl-beta-D-fructopyranose 1,2':2,1'-dianhydride, respectively.

摘要

通过将异构糖基果糖帕拉金糖、异麦芽糖、麦芽酮糖、乳酮糖和松二糖溶解于无水氟化氢中，分别以制备规模获得了双螺二氧杂环己烷基假四糖6-O-α-D-吡喃葡萄糖基-α-D-呋喃果糖6-O-α-D-吡喃葡萄糖基-β-D-呋喃果糖1,2':2,1'-二酐、5-O-α-D-吡喃葡萄糖基-α-D-吡喃果糖5-O-α-D-吡喃葡萄糖基-β-D-吡喃果糖1,2':2,1'-二酐、4-O-α-D-吡喃葡萄糖基-α-D-呋喃果糖4-O-α-D-吡喃葡萄糖基-β-D-吡喃果糖1,2':2,1'-二酐、4-O-β-D-吡喃半乳糖基-α-D-呋喃果糖4-O-β-D-吡喃半乳糖基-β-D-吡喃果糖1,2':2,1'-二酐以及3-O-α-D-吡喃葡萄糖基-α-D-呋喃果糖3-O-α-D-吡喃葡萄糖基-β-D-呋喃果糖1,2':2,1'-二酐。该反应涉及果糖单元游离异头位置的选择性质子化，已扩展至由帕拉金糖和果糖制备假三糖6-O-α-D-吡喃葡萄糖基-α-D-呋喃果糖β-D-吡喃果糖1,2':2',1-二酐，并使用松二糖和麦芽酮糖作为二糖前体制备其3-O-、4-O-和4'-O-葡萄糖基类似物。帕拉金糖与麦芽酮糖以及与异麦芽糖的交叉反应分别导致制备出6-O-α-D-吡喃葡萄糖基-α-D-呋喃果糖4-O-α-D-吡喃葡萄糖基-β-D-吡喃果糖1,2':2,1'-二酐和6-O-α-D-吡喃葡萄糖基-α-D-呋喃果糖5-O-α-D-吡喃葡萄糖基-β-D-吡喃果糖1,2':2,1'-二酐。