基于硅胶负载高氯酸(HClO4-SiO2)的固氮螺菌四糖重复单元的高效合成  

High Efficiency Synthesis of the Tetrasccharide Repeating Unit in Azospirillum brasilense Strains Sp246 Based on Silica Gel Supported Perchloric Acid(HClO4-SiO2)

作　　者：陈自力 李培霞 刘伟童 庄喆 武源源 赵汗青[1] 张建军[2] Chen Zili;Li Peixia;Liu Weitong;Zhuang Zhe;Wu Yuanyuan;Zhao Hanqing;Zhang Jianjun(Key Laboratory for Northern Urban Agriculture of Ministry of Agriculture and Rural Affairs,Beijing University of Agriculture,Beijing 102206;School of Science,China Agricultural University,Beijing 100193)

机构地区：[1]北京农学院农业农村部华北都市农业重点实验室,北京102206 [2]中国农业大学理学院,北京100193

出　　处：《有机化学》2020年第6期1716-1724,共9页Chinese Journal of Organic Chemistry

基　　金：北京市自然科学基金(No.2194072);国家自然科学基金(No.21772230);北京市教育委员会科技计划一般项目(No.KM201710020003);北京金桥工程种子基金(No.JQ18029);北京农学院青年教师科研基金(No.SXQN201801);北京农学院学位与研究生教育改革与发展项目(No.2019YJS028);北京农学院内涵发展定额大学生科研训练(No.KX2019001)资助项目。

摘　　要：以2,3,4-三-O-苯甲酰基-α-L-鼠李糖三氯乙酰亚胺酯、2,4-二-O-苯甲酰基-α-L-鼠李糖对甲氧基苯基苷、2,3,4,6-四-O-苯甲酰基-β-D-葡萄糖三氯乙酰亚胺酯和2,3-O-异丙叉基-α-L-鼠李糖对甲氧基苯基苷为原料,采用[2+2]偶联策略,对巴西固氮螺菌(Azospirillum brasilense type strain Sp246)表面脂多糖的四糖重复单元α-L-鼠李糖-(1→3)-α-L-鼠李糖-(1→3)-[β-D-葡萄糖-(1→4)]-α-L-鼠李糖结构进行全合成.在合成单元子的反应中,采用硅胶负载高氯酸(HClO4-SiO2)作为酸性催化剂,三乙基硅基作为选择性保护基,简单高效地构建全保护的四糖.该合成路线步骤短,试剂种类少,反应后处理简单,以L-鼠李糖为原料计算,目标化合物四糖总收率达到23%,化合物结构经~1H NMR和^(13)C NMR、HRMS和IR确证.A natural tetrasaccharide ofα-L-Rhap-(1→3)-α-L-Rhap-(1→3)-[β-D-Glup-(1→4)-]α-L-Rhap was synthesized via[2+2]assembly from 2,3,4-tri-O-benzoyl-α-L-rhamnopyranosyl trichloroacetimidate,p-methoxyphenyl 2,4-di-O-benzoyl-α-L-rhamnopyranoside,2,3,4,6-tetra-O-benzoyl-b-D-glucopyranosyl trichloroacetimidate and p-methoxyphenyl 2,3-O-isopropyl-α-L-rhamnopyranoside.This tetrasaccharide is a repeating unit of the lipopolisaccharides of the nitrogen fixing bacterium Azospirillum brasilense Sp246.In the reaction of the synthesis unit,silica gel loaded perchloric acid(HClO4-SiO2)was used as acid catalyst,and triethylsilyl group was used as selective protective group to construct a fully protected tetrasaccharide.The synthetic route is short,the reagents are few,and the post-processing is simple.The total yield of target tetrasaccharide is 23%based on L-rhamnose.The structures of the tetrasaccharide were confirmed by 1 H NMR,13C NMR,HRMS and IR spectra.

关 键 词：鼠李糖 硅胶负载高氯酸(HClO4-SiO2) 固氮螺菌 寡糖合成 

分 类 号：O629.12[理学—有机化学]