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

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.

The impact of alkali and alkaline earth metals on green ammonia synthesis

“…45,101 Moreover, a catalytic process for synthesizing N-containing chemicals, such as diarylamines, triarylamines, and N-heterocycles, from N 2 has been developed by Shi et al very recently, where Li 3 N, generated in situ by reacting Li with N 2 , supplies reactive N species to react with organohalides for constructing C-N bonds. 102 We believe that the above discussions/understandings of AM in ammonia synthesis would stimulate ideas and research efforts on N 2 functionalization as well.…”

Nitrogen fixation and transformation with main group elements

“…48–50 Recently, we developed a one-pot/two-step protocol to afford diarylamines, triarylamines and N-heterocycles from organohalides using N 2 as the nitrogen source (Scheme 1). 51 The in situ formed Li 3 N is a key intermediate in the Pd-catalyzed C–N coupling protocol.…”

Dinitrogen Functionalization Affording Structurally Well-Defined Cobalt Diazenido Complexes

“…[4][5][6] Early transition-metal N 2 complexes display rich reactivity with respect to electrophilic attack at the terminal N atom. [7][8][9][10][11][12][13][14][15][16][17][18][19][20][21][22][23][24] In comparison, there are fewer examples of N 2 functionalization of late transition-metal N 2 complexes, besides iron complexes. [25][26][27][28][29][30][31][32][33] The N 2 lability and electronegativity are strongly dependent on the metal's oxidation state, overall charge, and identity of the supporting ligands surrounding the metal center.…”