手性试剂(R)-β-甲基-γ-丁内酯及其衍生物的合成  

Synthesis of chiral reagent (R)-β-methyl-γ-butyrolactone and its derivatives

作　　者：程利利[1] 顾春燕[1] 李敏[1] 金荣华[1] 林静容[1] 田伟生[1,2] 

机构地区：[1]上海师范大学资源化学实验室,上海200234 [2]中国科学院上海有机化学研究所,上海200032

出　　处：《化学试剂》2010年第4期305-307,共3页Chemical Reagents

基　　金：上海市教育委员会科研创新项目(08YZ70;09Y164);上海师范大学前瞻性科研项目(DYL200903);上海师范大学一般科研项目(SK200721)

摘　　要：以剑麻皂甙元为原料,经氧化降解得到了手性目标化合物。再与溴化氢/无水乙醇反应,以86%的收率得到(R)-4-溴-3-甲基丁酸乙酯;当目标化合物与苄溴/氢氧化钠反应时,可选择性地分别以91%和90%的收率得到(R)-4-苄氧基-3-甲基丁酸和(R)-4-苄氧基-3-甲基丁酸苄酯。合成产物的结构采用IR、1HNMR和MS等确认。它们不仅为药物和生物活性天然化合物的合成提供了新的合成中间体,也为它们的新合成途径设计提供了机遇。（R）-β-Methyl-γ-butyrolactone,a chiral building block,was obtained from the waste resulted from the degradation of tigogenin.Ethyl （R）-4-bromo-3-methyl butyrate was synthesized via the reaction of （R）-β-methyl-γ-butyrolactone with HBr/EtOH in 86% yield,and the compound were chemo-selectively converted into （R）-4-benzyloxy-3-methylbutanoic acid and benzyl （R）-4-benzyloxy-3-methyl butyrate by the reaction with BnBr/NaOH in 91% and 90% yields,respectively.The structures of the products were confirmed by IR,^1HNMR and MS.These chiral reagents not only provide the important intermediates for the synthesis of chiral drugs and the optically active natural compounds,they also offer the opportunities for design of new synthetic routes.

关 键 词：剑麻皂甙元 (R)-β-甲基-γ-丁内酯 (R)-4-溴-3-甲基丁酸乙酯 (R)-4-苄氧基-3-甲基丁酸 (R)-4-苄氧基-3-甲基丁酸苄酯 

分 类 号：S432.4[农业科学—植物病理学]