保护的二糖半乳糖基(α1→2)葡萄糖的立体选择性合成  

Stereoselective Synthesis of Protected Galactopyranosyl(α1→2)Glucopyranoside

作　　者：陈朗秋[1] 史慎德[1] 夏殊[1] 罗军奇[1] 卢高超[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》2011年第8期630-634,共5页Chinese Pharmaceutical Journal

基　　金：湖南省自然科学基金资助项目(10JJ6023和05JJ40054)

摘　　要：目的获取具有1,2-顺式半乳糖苷键的带有易于选择性脱除的保护基的二糖半乳糖基(α1→2)葡萄糖片段。方法以D-半乳糖和D-葡萄糖为原料,采用多种保护方法与偶联策略,合成保护的二糖甲基-2-O-苯甲酰基-3-O-烯丙基-4,6-O-苯亚甲基-α-D-半乳吡喃糖基-(1→2)-3,4,6-三-O-苯甲酰基-α-D-葡萄吡喃糖苷(11)。结果来源于D-葡萄糖的甲基-4,6-O-苯亚甲基-α-D-葡萄吡喃糖苷依次通过选择性乙酰化、苯甲酰化、脱苯亚甲基、苯甲酰化、选择性脱乙酰基,得到甲基-3,4,6-三-O-苯甲酰基-α-D-葡萄吡喃糖苷。由D-半乳糖所合成的供体异丙基-2-O-苯甲酰基-3-O-烯丙基-4,6-O-苯亚甲基-β-D-1-硫代半乳吡喃糖苷与受体甲基-3,4,6-三-O-苯甲酰基-α-D-葡萄吡喃糖苷偶联,获得了甲基-2-O-苯甲酰基-3-O-烯丙基-4,6-O-苯亚甲基-α-D-半乳吡喃糖基-(1→2)-3,4,6-三-O-苯甲酰基-α-D-葡萄吡喃糖苷和甲基-2-O-苯甲酰基-3-O-烯丙基-4,6-O-苯亚甲基-β-D-半乳吡喃糖基-(1→2)-3,4,6-三-O-苯甲酰基-α-D-葡萄吡喃糖苷,α-半乳糖苷键联接与β-半乳糖苷键联接的立体选择性达到了3∶1,所有产物经NMR、MS等确证。结论首次完成了保护的二糖半乳糖基(α1→2)葡萄糖片段甲基-2-O-苯甲酰基-3-O-烯丙基-4,6-O-苯亚甲基-α-D-半乳吡喃糖基-(1→2)-3,4,6-三-O-苯甲酰基-α-D-葡萄吡喃糖苷的立体选择性合成。OBJECTIVE To achieve a protected disaccharide galactopyranosyl （α1→2） glucopyranoside fragment with a 1,2-cis galactosyl linkage and protected groups easily selectively deprotected. METHODS Through multiple protecting and coupling protocol, methyl 3-O-allyl-2-O-beuzoyl-4,6-O-benzylidene-ct-D-galactopyranosyl- （ 1→2 ） -3,4,6-tri-O-benzoyl-α-D-glucopyranoside （ 11 ） was synthesized with D-galactose and D-glucose as raw materials. RESULTS Methyl 3,4,6-tri-0-benzoyl-α-D-glucopyranoside was achieved via selective acetylation, benzoylation, debenzylidenation, benzoylation and selective deacetylation of methyl 4,6-O-benzyli- dene-α-D-glucopyranoside from D-glucose. A donor isopropyl 3-O-allyl-2-O-benzoyl-4,6-O-benzylidene-l-thio-β-D-galactopyranoside from D-galactose and an acceptor methyl 3,4,6-tri-O-benzoyl-α-D-glucopyranoside were coupled to obtain methyl 3-O-allyl-2-O-benzo- yl-4,6-0-benzylidene-α-D-galactopyranosyl-（1→2）-3,4,6-tri-O-benzoyl-α-D-glucopyranoside and methyl 3-O-allyl-2-O-benzoyl-4,6- O-benzylidene-β-D-galactopyranosyl-（ 1→2 ） -3,4,6-tri-O-benzoyl-α-D-glucopyranoside, and the stereoselective ratio of α-galaetosyl linkage to β-galactosyl linkage was 3： 1. All products were characterized with NMR, MS etc. CONCLUSION The protected disac- charide Gal （ α1→2 ） Glc fragment 3-O-allyl-2-O-benzoyl-4,6 -O-benzylidene-α-D-galactopyranosyl- （1→2） -3,4,6 -tri -O-benzoyl-α-D- glucopyranoside was stereoselectively synthesized for the first time.

关 键 词：半乳糖 葡萄糖 半乳糖基(α1→2)葡萄糖 合成 立体选择性 

分 类 号：R914.4[医药卫生—药物化学]