四丁基碘化胺催化活化烯烃烷氧羰基化反应合成异喹啉二酮衍生物有机化学.pdfVIP

DOI: 10.6023/cjoc201410015 研究论文 有机化学 Chinese Journal of Organic Chemistry ARTICLE 四丁基碘化胺催化活化烯烃烷氧羰基化反应: 合成异喹啉二酮衍生物 唐裕才 张 敏 李小青 许响生 杜晓华* (浙江工业大学化学工程学院 杭州 310014) 摘要 异喹啉二酮骨架是一种重要的有机合成砌块, 广泛存在于生物碱、天然产物和药物中. 提供了一种非金属催化 构建异喹啉二酮骨架结构的新方法. 机理研究表明, 该反应经历了一个自由基过程: 在四丁基碘化胺催化作用下, 肼 化合物质子被逐步攫取生成烷氧羰基自由基, 随后对活化烯烃进行自由基加成反应, 进一步环化形成异喹啉二酮骨架. 该方法具有反应条件温和、底物普适性广、环境友好等特点, 为合成含异喹啉二酮骨架分子结构提供了一种新途径. 关键词 异喹啉二酮结构; 非金属催化; 四丁基碘化胺; 自由基加成/环化 Tetrabutylammonium Iodide-Catalyzed Radical Alkoxycarbonylation of Activated Alkenes: Synthesis of Isoquinolinedione Derivatives Tang, Yucai Zhang, Min Li, Xiaoqing Xu, Xiangsheng Du, Xiaohua* (College of Chemical Engineering, Zhejiang University of Technology, Hangzhou 310014) Abstract The isoquinolinedione skeletons are important building blocks, which have been widely present in plant alkaloids, natural products and pharmaceuticals. In this paper, a novel method to construct isoquinolinedione framework was developed, which can be easily operated under metal-free conditions. In the presence of tetrabutylammonium-iodide catalyst, hydrogen atoms were abstracted step by step from carbazate to generate methoxycarbonyl radical which followed by radical addition/ cyclization reaction leading to isoquinolinedione. The presented methodology will provide new strategies for construct iso- quinolinedione-type products, which has advantages of simple operation, mild reaction conditions, and environmentally be- nign. Keywords isoquinolinedione skeleton; metal-free; tetrabutylammonium-iodide; radical addition/cyclization 异喹啉二酮