Synthesis of arylamines and N-heterocycles by direct catalytic nitrogenation using N2

• Published in: Nature communications Vol. 12; no. 1; p. 248
• Main Authors: Wang, Kai, Deng, Zi-Hao, Xie, Si-Jun, Zhai, Dan-Dan, Fang, Hua-Yi, Shi, Zhang-Jie
• Format: Journal Article
• Language: English
• Published: London Nature Publishing Group UK 11.01.2021; Nature Publishing Group; Nature Portfolio
• Subjects: 140/131; 140/146; 639/638/549/884; 639/638/549/933; 639/638/77/888; Amines; Ammonia; Chemical industry; Chemical synthesis; Chemicals; Humanities and Social Sciences; Lithium; multidisciplinary; Nitric acid; Nitrogen; Nitrogen atoms; Nitrogenation; Organic chemistry; Organic compounds; Oxidation; Polyanilines; Reducing agents; Science; Science (multidisciplinary)
• ISSN: 2041-1723; 2041-1723
• DOI: 10.1038/s41467-020-20270-5

Ammonia and nitric acid are two key platform chemicals to introduce nitrogen atoms into organic molecules in chemical industry. Indeed, nitric acid is mostly produced through the oxidation of ammonia. The ideal nitrogenation would involve direct use of dinitrogen (N 2 ) as a N source to construct N-containing organic molecules. Herein, we report an example of direct catalytic nitrogenation to afford valuable diarylamines, triarylamines, and N-heterocycles from easily available organohalides using dinitrogen (N 2 ) as the nitrogen source in a one-pot/two-step protocol. With this method, 15 N atoms are easily incorporated into organic molecules. Structurally diversified polyanilines are also generated in one pot, showing great potential for materials chemistry. In this protocol, lithium nitride, generated in situ with the use of lithium as a reductant, is confirmed as a key intermediate. This chemistry provides an alternative pathway for catalytic nitrogenation to synthesize highly valuable N-containing chemicals from dinitrogen. Ammonia and nitric acid are key platform chemicals to introduce nitrogen into organic molecules, however gaseous N 2 would be a more direct and available source of nitrogen. Here, the authors report a direct catalytic nitrogenation to afford valuable arylamines and N-heterocycles from organohalides using dinitrogen (N 2 ) as the nitrogen source.