Selective Cross-Coupling of (Hetero)aryl Halides with Ammonia To Produce Primary Arylamines using Pd-NHC Complexes

Herein we report the first example of (hetero)-arylation of ammonia using a monoligated palladium-NHC complex. The new, rationally designed, precatalyst (DiMeIHept(Cl))Pd(allyl)Cl featuring highly branched alkyl chains has been shown to be effective in selective aminations across a range of challenging substrates, including nitrogen containing heterocycles and those featuring base-sensitive functionality. The less bulky Pd-PEPPSI-IPent(Cl) precatalyst performs well for ortho-substituted aryl halides, giving monoarylated products in high yield with good selectivity.