Affiliation:
1. Northeast Normal University
2. University of Pavia
3. University of Oxford
Abstract
Abstract
The conversion of inexpensive aqueous ammonia (NH3·H2O) into value-added primary amines by N − H insertion persists as a longstanding challenge in chemistry because of the tendency of Lewis basic ammonia (NH3) to bind and inhibit metal catalysts. Herein, we report a chemoselective carbene N − H insertion of NH3·H2O using a TpBr3Ag-catalyzed two-phase system. Weak coordination by a homoscorpionate ligand enables silver compatible with NH3 and H2O and ensures the generation of electrophilic silver carbene. Water promotes subsequent [1, 2]-proton shift to generate N − H insertion mono-substituted products with high chemoselectivity. The end 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.
Publisher
Research Square Platform LLC
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