(3S，4R)-3，4-(二氧丙叉基)-N-氧化吡咯烷与丙烯酸甲酯的环加成反应研究  

Study on 1,3-Dipolar Cycloaddition Reaction of (3S,4R)-3,4-Isoprorylidenedioxy-1-pyrroline N-oxide with Methyl Acrylate

作　　者：李欣[1] 林智杰[1] 胡泓梵[1] 张洪奎[1] 

机构地区：[1]厦门大学化学化工学院,化学生物学福建省重点实验室,福建厦门361005

出　　处：《厦门大学学报（自然科学版）》2009年第1期64-68,共5页Journal of Xiamen University：Natural Science

基　　金：国家基础科学人才培养基金(J0630429);福建省高校创新团队项目资助

摘　　要：硝酮与烯烃的的1,3-偶极环加成反应是构成五元含氮杂环的重要方法.本文先由异抗坏血酸经H2O2氧化,合成了(2R,3R)-(O,O-丙叉基)-γ-丁内酯1,然后用"一锅煮"的实验方法经DIBAL-H还原,羟胺化及甲磺酸处理,以55%的产率制备了环状硝酮2.接着,研究了环状硝酮2与丙烯酸甲酯3的1,3-偶极环加成反应.实验结果表明:当反应在甲苯中于室温下搅拌1.5 h,得到了区域选择性的环加成产物4a和4b,产率为76%.产物的波谱分析指出:该环加成反应具有高度的区域选择性和立体选择性,但endo/exo选择性较差(1:1.3).1,3-Dipolar eycloaddition reaction of nitrone with olefin is an important method for constructing nitrogen-containing five-membered hetereocycles. First, cyclic nitrone 2 was prepared in 55% yield, with starting from D-isoascorbic acid,by oxidation with H2O, ,followed by treatment of（3S, 4R）-3,4-isoprorylidenedioxy-γ-butyrolactone 1 with DIBAL-H, hydroxylamine and methanesulfonyl chloride in one-pot procedure. Then, 1,3-Dipolar cycloaddition reaction of cyclic nitrone 2 with methyl acrylate 3 was investigated. The reaction was underwent smoothly at room temperature in toluene for 1.5 h to afford the corresponding cycloadduts isoxazolidines 4a and 4b in 76 % yield. Moreover, high regio- and stereo-selectivities were achieved in this reaction. However,low endo/exo selectivity with ratio of 1 ： 1.3 was observed.

关 键 词：环状硝酮 丙烯酸甲酯 (3S 4R)-3 4-(二氧丙叉基)-N-氧化吡咯烷 1 3-偶极环加成反应 

分 类 号：O621.3[理学—有机化学]