Dao Pham Duy Quang, Lee Seong Weon, Lim Ho-Jin, Cho Chan Sik
Institute of Applied Materials Science, Vietnam Academy of Science and Technology, Ho Chi Minh City 700000, Vietnam.
Department of Applied Chemistry, Kyungpook National University, 80 Daehakro, Bukgu, Daegu 41566, Republic of Korea.
J Org Chem. 2024 Dec 20;89(24):18556-18564. doi: 10.1021/acs.joc.4c02496. Epub 2024 Dec 4.
In this study, 5-(2-bromoaryl)tetrazoles were reacted with 1,3-diketones in DMF in the presence of a catalytic amount of magnetic Cu-MOF-74 (FeO@SiO@Cu-MOF-74) and a base under microwave irradiation to yield the corresponding 1-aminoisoquinolines. The FeO@SiO@Cu-MOF-74 catalyst could be easily recovered from the reaction mixture and reused four times without any significant loss of catalytic activity. An initial copper-catalyzed C(sp)-C(sp) bond formation accompanied by -Claisen deacylative cyclocondensation (for acyclic 1,3-diketones) and direct cyclocondensation (for cyclohexane-1,3-diones) is proposed as a key reaction pathway for this process. Cyclohexanone-fused 1-aminoisoquinolines produced from the reaction between 5-(2-bromoaryl)tetrazoles and cyclohexane-1,3-diones could be aromatized into 6-aminophenanthridines via a one-pot sequential process involving reduction, dehydration, and oxidation.
在本研究中，5-(2-溴芳基)四唑在催化量的磁性Cu-MOF-74（FeO@SiO@Cu-MOF-74）和碱存在下，于N,N-二甲基甲酰胺（DMF）中与1,3-二酮在微波辐射下反应，生成相应的1-氨基异喹啉。FeO@SiO@Cu-MOF-74催化剂可轻松从反应混合物中回收，并重复使用四次，且催化活性无任何显著损失。提出了一种初始的铜催化C(sp)-C(sp)键形成过程，该过程伴随着-Claisen脱酰环化缩合反应（对于无环1,3-二酮）和直接环化缩合反应（对于环己烷-1,3-二酮），这是该过程的关键反应途径。由5-(2-溴芳基)四唑与环己烷-1,3-二酮反应生成的环己酮稠合的1-氨基异喹啉可通过一锅法连续过程（包括还原、脱水和氧化）芳构化为6-氨基菲啶。
