Chemoselective carbene insertion into the N−H bonds of NH3·H2O

• Published in: Nature communications 2022-12, Vol.13 (1), p.7649-7649, Article 7649
• Main Authors: Liu, Zhaohong, Yang, Yong, Song, Qingmin, Li, Linxuan, Zanoni, Giuseppe, Liu, Shaopeng, Xiang, Meng, Anderson, Edward A., Bi, Xihe
• Format: Article
• Language: English
• Subjects: 119/118; 639/638/263/406; 639/638/403/933; 639/638/77/885; Amines; Ammonia; Binary systems; Carbenes; Catalysts; Coupling (molecular); Humanities and Social Sciences; Insertion; multidisciplinary; Nitrogen; Organic chemicals; Organic chemistry; Reaction mechanisms; Science; Science (multidisciplinary); Silver
• ISSN: 2041-1723; 2041-1723
• DOI: 10.1038/s41467-022-35394-z

The conversion of inexpensive aqueous ammonia (NH 3 ·H 2 O) into value-added primary amines by N−H insertion persists as a longstanding challenge in chemistry because of the tendency of Lewis basic ammonia (NH 3 ) to bind and inhibit metal catalysts. Herein, we report a chemoselective carbene N−H insertion of NH 3 ·H 2 O using a Tp Br3 Ag-catalyzed two-phase system. Coordination by a homoscorpionate Tp Br3 ligand renders silver compatible with NH 3 and H 2 O and enables the generation of electrophilic silver carbene. Water promotes subsequent [1,2]-proton shift to generate N−H insertion products with high chemoselectivity. The result of the reaction is the coupling of an inorganic nitrogen source with either diazo compounds or N- triftosylhydrazones to produce useful primary amines. Further investigations elucidate the reaction mechanism and the origin of chemoselectivity. Converting low-cost inorganic chemicals into value-added organic chemicals is a longstanding goal in chemistry. Here the authors describe a silver-catalysed chemoselective carbene N−H insertion reaction, providing access to primary amines from aqueous ammonia and diazo compounds.