保护的半乳糖基(α1→2)葡萄糖苷中间体的立体专一性合成  

Stereospecific Synthesis of Protected Gal(α1→2)Glc

作　　者：唐秋娥[1] 史慎德[1] 陈朗秋[1] 卢高超[1] 曾森[1] 刘玉苗[1] 

机构地区：[1]湘潭大学化学学院环境友好化学与应用省部共建教育部重点实验室,湖南湘潭411105

出　　处：《中国药学杂志》2012年第19期1592-1597,共6页Chinese Pharmaceutical Journal

基　　金：湖南省自然科学基金资助项目(10JJ6023;05JJ40054);湘潭大学第七批大学生创新基金研究项目(54);博士科研启动费(05QDZ09)

摘　　要：目的立体专一性地合成带有易于选择性地脱除的保护基的二糖半乳糖基(α1→2)葡萄糖苷片段。方法以D-葡萄糖为原料,经过乙酰化、溴代、甲基化、脱乙酰基、苯亚甲基化、选择性苯甲酰化、氯乙酰化、脱氯乙酰基,合成甲基-3,4,6-三-O-苯甲酰基-β-D-葡萄糖苷;该葡萄糖苷受体与供体异丙基-2-O-苯甲酰基-3-O-烯丙基-4,6-O-苯亚甲基-β-D-1-硫代半乳糖苷在催化剂作用下反应,获取α-偶联的二糖产物。结果半乳糖供体与葡萄糖受体在TMSOTf/NIS的催化下偶联,立体专一性地得到了全保护的二糖半乳糖基(α1→2)葡萄糖苷片段甲基-2-O-苯甲酰基-3-O-烯丙基-4,6-O-苯亚甲基-α-D-半乳糖基(1→2)-3,4,6-三-O-苯甲酰基-β-D-葡萄糖苷,产品经NMR、MS确证。结论在半乳糖供体和葡萄糖受体的特定结构的共同影响下,立体专一性地获得了全保护的1,2-顺式的二糖片段。OBJECTIVE To stereospecifically synthesize disaccharide galactopyranosyl （α1→2）glucopyranoside with protecting groups which are easily and selectively deprotected. METHODS With D-glucose as a raw material, a donor methyl 3,4,6-tri-O-ben- zoyl--D-glucopyranoside was synthesized through acetylation, bromination, methylation, deacetylation, benzylidenation, selective benzoylation, chloroacetylation, and dechloroacetylation ; the glucopyranosyl acceptor and a donor isopropyl 3-O-allyl-2-O-benzoyl-4,6- O-benzylidene-β-D-l-thiogalactopyranoside were reacted at catalysis to achieve an α-coupled product. RESULTS At the catalysis of TMSOTf/NIS, galactopyranosyl donor and glucopyranosyl acceptor were coupled to afford stereospecifically a full protected disaccharide galactopyranosyl（α1→2）glucopyranoside fragment, methyl 3-O-allyl-2-O-benzoyl-4,6-O-benzylidene-a-D-galactopyranosyl（ 1-→2）-3, 4,6-tri-O-benzoyl-β-D-glucopyranoside. All products were characterized with NMR and MS etc. CONCLUSION A full protected 1, 2-cis disaeeharide fragment was stereospecifieally obtained through coupling reaction due to concerted effect of the special configurations of the galactopyranosyl donor and the glucopyranosyl acceptor.

关 键 词：半乳糖 葡萄糖 半乳糖基(α1→2)葡萄糖 合成 立体专一性 

分 类 号：R914.4[医药卫生—药物化学]