用于立体选择性合成Kdo-α-糖苷的异头中心O-烷基化反应

O-alkylation at the anomeric centre for the stereoselective synthesis of Kdo-alpha-glycosides.

作者信息

Esswein A, Rembold H, Schmidt R R

机构信息

Fakultät für Chemie, Universität Konstanz, F.R.G.

出版信息

Carbohydr Res. 1990 Apr 25;200:287-305. doi: 10.1016/0008-6215(90)84198-4.

DOI:10.1016/0008-6215(90)84198-4

PMID:2379210

Abstract

O-Alkylation at the anomeric centre of the dianion of 4,5:7,8-di-O-cyclohexylidene-3-deoxy-N-methyl-alpha-D-manno- octulopyranosonamide (1) with several triflates led diastereoselectively to the alpha-glycosides. In this way, lipopolysaccharide building-blocks containing alpha-Kdo-(2----6)-GlcN and alpha-Kdo-(2----6)-beta-GlcN-(1----6)-GlcN moieties were obtained and deployed in the synthesis of decyl 4,5,7,8-tetra-O-acetyl-3-deoxy-N-methyl-alpha-D-manno-2-octulopyranos idonamide (18), 2,3-di-O-tetradecanoyl-D-glycer-1-yl 4,5,7,8-tetra-O-acetyl-3-deoxy-N-methyl- alpha-D-manno-2-octulopyranosid-onamide (22), methyl 2,3,4-tri-O-acetyl-6-O-(methyl 4,5,7,8-tetra-O-acetyl-3-deoxy-alpha-D- manno-2-octulopyranosylonate)-alpha-D-glucopyranoside (28), 1-O-acetyl-2-deoxy-6-O-(methyl 4,5,7,8-tetra-O-acetyl-3-deoxy-alpha-D-manno-2- octulopyranosylonate)-2-tetradecanoylamino-alpha-D-glucopyra nose (33), tert-butyldimethylsilyl O-(methyl 4,5:7,8-di-O-cyclohexylidene-3-deoxy-alpha-D- manno-2-octulopyranosylonate)-(2----6)-O-(3,4-di-O-benzyl-2-deoxy- 2- tetradecanoylamino-beta-D-glucopyranosyl)-(1----6)-3,4-di-O-benzyl -2-deoxy-2- tetradecanoylamino-alpha-D-glucopyranoside (36).

摘要

4,5:7,8-二-O-环己叉基-3-脱氧-N-甲基-α-D-甘露辛吡喃糖酰胺（1）的双负离子在异头中心处与几种三氟甲磺酸酯进行O-烷基化反应，非对映选择性地生成α-糖苷。通过这种方式，获得了含有α-Kdo-(2→6)-GlcN和α-Kdo-(2→6)-β-GlcN-(1→6)-GlcN部分的脂多糖构建块，并将其用于合成癸基4,5,7,8-四-O-乙酰基-3-脱氧-N-甲基-α-D-甘露-2-辛吡喃糖酰胺（18）、2,3-二-O-十四烷酰基-D-甘油-1-基4,5,7,8-四-O-乙酰基-3-脱氧-N-甲基-α-D-甘露-2-辛吡喃糖酰胺（22）、甲基2,3,4-三-O-乙酰基-6-O-（甲基4,5,7,8-四-O-乙酰基-3-脱氧-α-D-甘露-2-辛吡喃糖酸酯）-α-D-吡喃葡萄糖苷（28）、1-O-乙酰基-2-脱氧-6-O-（甲基4,5,7,8-四-O-乙酰基-3-脱氧-α-D-甘露-2-辛吡喃糖酸酯）-2-十四烷酰氨基-α-D-吡喃葡萄糖苷（33）、叔丁基二甲基甲硅烷基O-（甲基4,5:7,8-二-O-环己叉基-3-脱氧-α-D-甘露-2-辛吡喃糖酸酯）-(2→6)-O-（3,4-二-O-苄基-2-脱氧-2-十四烷酰氨基-β-D-吡喃葡萄糖基）-(1→6)-3,4-二-O-苄基-(-2-脱氧-2-十四烷酰氨基-α-D-吡喃葡萄糖苷（36）。