纳米碘化亚铜催化杂环C—H烯基化反应
收稿日期: 2015-05-26
修回日期: 2015-07-26
网络出版日期: 2015-08-25
基金资助
国家自然科学基金(Nos. 20972002, 21272006)资助项目.
Alkenylation of Heterocycle C—H Catalyzed by CuI Nanoparticles
Received date: 2015-05-26
Revised date: 2015-07-26
Online published: 2015-08-25
Supported by
Project supported by the National Natural Science Foundation of China (Nos. 20972002, 21272006).
杂环是一类非常重要的有机化合物, 存在于许多天然产物和人工合成的化合物中. 其中烯基化杂环化合物不仅可以作为某些高活性聚合物分子的单体, 而且在药物、光电材料等合成方面都有非常重要的应用价值. 发展了以纳米碘化亚铜为催化剂, 磷酸钾为碱, 1,10-邻啡啰啉为配体, 二乙二醇二甲醚为溶剂, 在氩气保护下加热回流24 h来促使杂环和溴代烯烃反应生成烯基化杂环化合物. 催化使用的纳米碘化亚铜制备简单, 性质稳定, 在反应后可以回收循环使用, 催化活性没有明显降低. 而且该催化体系适用于多种芳香杂环, 杂环C—H键酸性越强, 越容易发生烯基化反应, 产率越高. 本工作共得到18个反式的烯基化杂环产物, 并对这些化合物进行了结构表征.
王园园 , 尤青 , 陶贵德 , 张新明 , 张武 . 纳米碘化亚铜催化杂环C—H烯基化反应[J]. 有机化学, 2015 , 35(10) : 2086 -2094 . DOI: 10.6023/cjoc201505037
The heterocycles and their derivatives are important organic compounds which are widely existed in various natural products and synthetic compounds. Alkenylated heterocycles have great value in the synthesis of natural products, medicine molecules, photoelectric materials and high active polymers. Herein, an efficient method was developed for C—H functionalization of heterocycles to synthesize alkenylated heterocycles with CuI nanoparticles as catalyst, K3PO4 as base, 1,10-phenanthroline as ligand, diglyme as solvent under reflux in argon atmosphere for 24 h. The CuI nanoparticles can be recycled and reused without any significant decrease in catalytic activity. In addition, various aromatic heterocycles can be applied to our catalytic system, and acidity of heterocycle C—H bonds is critical to the reactivity. 18 corresponding trans-alkenylated heterocycles were obtained and characterized.
Key words： heterocycle; alkenylation; CuI nanoparticles; recycle
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