Synthesis of Diarylamines via Nitrosonium-Initiated C–N Bond Formation
Pin‐Hsien Chen, Shu‐Jung Hsu, Cheng‐Chun Chen, Jui‐Chen Fu, Duen‐Ren Hou
Abstract
High Resolution Image Download MS PowerPoint Slide Electron-rich diarylamines, exemplified by anisole-derived amines, play pivotal roles in process chemistry, pharmaceuticals, and materials. In this study, homo-diarylamines were synthesized directly from the C–H activation of electron-rich arenes by sodium nitrate/trifluoroacetic acid and the successive treatment of iron powder. Mechanistic investigations reveal that nitrosoarene serves as the reaction intermediate, and the formation of the second C–N bond between the resulting nitrosoarene and electron-rich arene is catalyzed by the nitrosonium ion (NO + ). Thus, hetero-diarylamines were synthesized using preformed nitrosoarenes and various electron-rich arenes. This reaction complements a range of cross-coupling reactions catalyzed by transition metal catalysts.