乙酸钙不动杆菌NCTC 10305脂多糖核心成分烯丙基O - [（α-D-甘油-D-塔罗-2-辛基吡喃糖基）酸钠] -（2→6）-2-乙酰氨基-2-脱氧-β-D-吡喃葡萄糖苷的合成

Synthesis of allyl O-[sodium(alpha-D-glycero-D-talo-2- octulopyranosyl)onate]-(2-->6)-2-acetamido-2-deoxy-beta-D-glucopyranosi de, a core constituent of the lipopolysaccharide from Acinetobacter calcoaceticus NCTC 10305.

作者信息

Gass J, Strobl M, Loibner A, Kosma P, Zähringer U

机构信息

Institut für Chemie, Universität für Bodenkultur, Wien, Austria.

出版信息

Carbohydr Res. 1993 May 21;244(1):69-84. doi: 10.1016/0008-6215(93)80005-y.

DOI:10.1016/0008-6215(93)80005-y

PMID:8339301

Abstract

Reaction of methyl 2,6-anhydro-2,3-dideoxy-D-manno-2-octenoate 1 with 3-chloroperoxybenzoic acid gave the 2,3-anhydro derivative 2, which was converted into the per-O-acetylated anomeric methyl glycosides of D-glycero-D-galacto-2-octulopyranosylonic acid in good yield. Subsequent inversion of the configuration at C-3 and deprotection afforded sodium (methyl beta-D-glycero-D-talo-2-octulopyranosid)onate. Alternatively, 2 was transformed into methyl (alpha-D-glycero-D-talo-2- octulopyranosyl bromide(onate derivatives. Reaction with methanol or allyl 2-acetamido-2-deoxy- 3,4-O-(1,1,3,3-tetraisopropyldisiloxan-1,3-diyl)-beta-D-g lycopyranoside, promoted by silver triflate, gave good yields of the corresponding orthoester derivatives. Me3Si triflate-catalyzed orthoester rearrangement and removal of the protecting groups afforded sodium O-(methyl alpha-D-glycero- D-talo-2-octulopyranosid)onate and the disacchanide, allyl O-[sodium(alpha-D-glycero-D-talo-2- octulopyranosyl)onate]-(2-->6)-2-acetamido-2-deoxy-beta-D-gl ucopyranoside in high yield.

摘要

2,6-脱水-2,3-二脱氧-D-甘露糖-2-辛烯酸甲酯1与3-氯过氧苯甲酸反应生成2,3-脱水衍生物2，该衍生物以良好的产率转化为D-甘油-D-半乳糖-2-辛酮糖酸的全-O-乙酰化异头甲基糖苷。随后C-3位构型翻转并脱保护得到（甲基β-D-甘油-D-塔罗-2-辛酮糖苷）酸钠。另外，2被转化为甲基（α-D-甘油-D-塔罗-2-辛酮糖基溴）（酸酯衍生物。在三氟甲磺酸银促进下与甲醇或烯丙基2-乙酰氨基-2-脱氧-3,4-O-（1,1,3,3-四异丙基二硅氧烷-1,3-二基）-β-D-吡喃葡萄糖苷反应，得到相应原酸酯衍生物的良好产率。三氟甲磺酸三甲基硅酯催化的原酸酯重排和保护基的去除以高产率得到O-（甲基α-D-甘油-D-塔罗-2-辛酮糖苷）酸钠和二糖烯丙基O-[（α-D-甘油-D-塔罗-2-辛酮糖基）酸钠]-(2→6)-2-乙酰氨基-2-脱氧-β-D-吡喃葡萄糖苷。