丙二腈及氰乙酸酯参与的3-脱氢莽草酸甲酯缩合-芳构化-环合串联反应  

Malononitrile and Cyanoacetic Acid Esters Involved Cascade Reaction of (-)-Methyl 3-Dehydroshikimate

作　　者：王德建[1,2] 张恩生[1,2] 徐田龙[1,2] 李军[3] 黄桐堃[1] 邹永[1,4] 

机构地区：[1]中国科学院广州化学研究所,广州510650 [2]中国科学院大学,北京100049 [3]浙江大学医学院附属第二医院,杭州313000 [4]中山大学药学院,广州510006

出　　处：《高等学校化学学报》2015年第2期267-273,共7页Chemical Journal of Chinese Universities

基　　金：国家自然科学基金(批准号:21272280;81301890);广东省自然科学基金(批准号:S2013010014278);广东省新药设计与评价重点实验室基金(批准号:2011A060901014);广州市科技计划项目(批准号:2014J4100224);浙江省自然科学基金(批准号:LY13H160010);浙江省中医药优秀青年人才基金(批准号:2012ZQ017)资助~~

摘　　要：3-脱氢莽草酸甲酯与丙二腈、氰乙酸乙酯及氰乙酸甲酯等活性亚甲基化合物在一定条件下发生缩合、芳构化及环合反应,可方便地构建C—C键并得到多取代的2-氨基苯并呋喃类化合物(3a^3e,4a和4b),其中化合物3a中的氰基和甲氧羰基可分别进行选择性水解.该方法具有原料易得、条件温和、操作简单及收率高等优点,为可再生生物质资源莽草酸的多样化转化和利用提供了新思路.With the diminishing of fossil oil reserves, chemical conversion and value-added utilization of re-newable biomass have become a worldwide topic for chemists. It was demonstrated that the reaction between （-）-methyl 3-dehydroshikimate （ 3-MDHS ） and several active methylene compounds under facile conditions gave rise to substituted 2-aminobenzofurans in moderate to good yields. The process involved the formation of a new C—C bond through condensation, followed by a sequential aromatization/cyclization reaction. The chemoselective hydrolysis of compound 3a was also realized. The structures of the synthesized compounds were characterized by 1 H NMR, 13 C NMR, MS and IR. The ready availability of biosourced starting materials, the convenient reaction conditions as well as the easy workup procedures made this protocol a practical method for the chemical conversion of the renewable biomass （-）-shikimic acid.

关 键 词：3-脱氢莽草酸甲酯 活性亚甲基化合物 2-氨基苯并呋喃 可再生生物质 

分 类 号：O626[理学—有机化学]