铜(Ⅰ)催化丙炔酸、仲胺、醛和甲醛一锅法交叉偶联构建非对称1,4-二氨基丁炔  

One-Pot Synthesis of Unsymmetrical 1,4-Diaminobutynes by Cu(Ⅰ)-Catalyzed Cross-Coupling of Propiolic Acid,Secondary Amine, Aldehydes and Formaldehyde

作　　者：刘博瑜 徐仙君 黄立梁[1] 冯煌迪 Liu Boyu;Xu Xianjun;Huang Liliang;Feng Huangdi(College of Chemistry and Chemical Engineering,Shanghai University of Engineering Science,Shanghai 201620)

机构地区：[1]上海工程技术大学化学化工学院,上海201620

出　　处：《有机化学》2020年第5期1290-1296,共7页Chinese Journal of Organic Chemistry

基　　金：上海市自然科学基金(No.15ZR1418800);中国博士后科学基金(No.2016M601681);上海工程技术大学(Nos.cs1704006,201810856017).

摘　　要：以丙炔酸、仲胺、烷基醛和甲醛为试剂,在过渡金属铜催化下高效地构建了一系列非对称1,4-二氨基-2-丁炔化合物.该多组分一锅二步方法历经A3-脱羧偶联生成关键中间体炔丙胺,随后该中间体加成到原位形成的亚胺离子上,最终以中等到优异的产率得到交叉偶联产物.该策略成功地将脂肪族仲胺引入到反应体系中,具有底物胺兼容性较好的特点.A highly selective and efficient copper-catalyzed sequential approach for the one-pot two-step synthesis of unsymmetrical 1,4-diamino-2-butynes from propiolic acid,secondary alkylamine,aldehyde and formaldehyde solution has been developed.The process of this reaction was involved in the generation of key intermediate propargylamines which were obtained via decarboxylative A3-coupling reaction.After that,the intermediate propargylamines would react with in situ formed iminium ions to give the cross-coupling target products in moderate to excellent yields under microwave irradiation.

关 键 词：非对称二氨基丁炔 脱羧偶联 A3-偶联 交叉偶联 铜催化 

分 类 号：O621.251[理学—有机化学]