Kai Wang1, Zi-Hao Deng1, Si-Jun Xie1, Dan-Dan Zhai1, Hua-Yi Fang1, Zhang-Jie Shi2,3. 1. Department of Chemistry, Fudan University, Shanghai, 200433, China. 2. Department of Chemistry, Fudan University, Shanghai, 200433, China. zjshi@fudan.edu.cn. 3. State Key Laboratory of Organometallic Chemistry, Shanghai Institute of Organic Chemistry, Chinese Academy of Sciences, Shanghai, 200032, China. zjshi@fudan.edu.cn.
Abstract
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 (N2) 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 (N2) as the nitrogen source in a one-pot/two-step protocol. With this method, 15N 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 n class="Chemical">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 (N2) 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 (N2) as the nitrogen source in a one-pot/two-step protocol. With this method, 15N 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.
Authors: Jingguang G Chen; Richard M Crooks; Lance C Seefeldt; Kara L Bren; R Morris Bullock; Marcetta Y Darensbourg; Patrick L Holland; Brian Hoffman; Michael J Janik; Anne K Jones; Mercouri G Kanatzidis; Paul King; Kyle M Lancaster; Sergei V Lymar; Peter Pfromm; William F Schneider; Richard R Schrock Journal: Science Date: 2018-05-25 Impact factor: 47.728