铜催化的碳二亚胺成胍反应高效构建胍类杂环衍生物  

Copper-Catalyzed Guanylation Reaction of Carbodiimides with Diaryliodonium Salts Constructing Heterocyclic Guanidines

作　　者：何思思 杨双兰 王岩 柳高 王连军[2] HE Si- si;YANG Shuang- lan;WANG Yan;LIU Gao;WANG Lian -jun(School of Education, Hunan University of Science and Technology, Xiangtan 411201, China;Chemistry and Chemical Engineering, Hunan Institute of Engineering, Xiangtan 411104, China)

机构地区：[1]湖南科技大学教育学院,湘潭411201 [2]湖南工程学院化学化工学院,湘潭411104

出　　处：《湖南工程学院学报（自然科学版）》2018年第3期69-75,共7页Journal of Hunan Institute of Engineering(Natural Science Edition)

基　　金：湖南省自科基金项目(2018JJ4049);湖南省高校创新平台开放基金项目(16K023)

摘　　要：以1,2-二氯乙烷为溶剂,以三氟甲磺酸亚铜为催化剂,催化碳二亚胺与二芳基碘鎓离子反应,高效地合成2-胺基嘧啶及2,4-二氨基喹唑啉等多种杂环化合物.该反应操作简单,原料易得,产物也具有一定的生物应用潜力,且对于不对称的底物也存在很好的选择性.研究表明该反应经历了一种特殊的脒类正离子中间体,经过"亲核进攻/1,5-氢迁移/1,7-氢迁移/6π-电环化/芳构化"这一系列步骤得到最终产物.该反应第一次实现了亚胺α′和β′位置三根C-H键的官能团化,并伴随C=N、CN键的断裂与C-N、C-C键的生成.A series of N heterocyclic guanidines 2 aminopyrimidines and 2,4 diaminoquinazolines are efficiently synthesized via reaction of Carbodiimides with diaryliodonium salts with C2 H4 Cl2 as solvent and CuOTf ·1/2C6H6 as catalyst. The reaction is simple; the raw material is easy to get; the products also have a certain potential biological application, and it also has good selectivity for the asymmetric sbstrate. Detailed research shows that the reaction experiences a special amidine cation intermediate, It undergoes C N formation/I, 5 H shift/l, 7 H shift/6π- ERC/aromatization. It is an important supplement in imine and C H bond functionalization chemistry. It is the first triple C（spa） H bond functionalization neighboring imine group, and involves C N, C=N bond cleavage and C N, C C bond formation.

关 键 词：成胍反应 碳二亚胺 碘鎓离子 杂环化合物 

分 类 号：TQ254.1[化学工程—有机化工]