Nucleophilic Amination of Aryl Halides with an Azanide Surrogate.

We report the development of an azanide (NH) surrogate which enables the facile conversion of electron-deficient (hetero)aryl halides into primary N-aryl amines under transition-metal-free conditions. The designed amidine reagent is easy to prepare, bench stable, and undergoes facile N-arylation under basic conditions at 40 °C. Intermediate N-aryl amidines are readily cleaved to form N-aryl amines in situ through hydrolysis or base-promoted elimination.

Manganese-Catalyzed Hydrofunctionalization of Alkenes.

The manganese-catalyzed hydrosilylation and hydroboration of alkenes has been developed using a single manganese(II) precatalyst and reaction protocol. Both reactions proceed with excellent control of regioselectivity and in high yields across a variety of sterically and electronically differentiated substrates (25 examples). Alkoxide activation, using NaO Bu, was key to precatalyst activation and reactivity.

AsCat and FurCat: new Pd catalysts for selective room-temperature Stille cross-couplings of benzyl chlorides with organostannanes.

Two novel succinimide-based palladium complexes, AsCat and FurCat, are highly efficient catalysts for room-temperature Stille cross-coupling of organostannanes with benzyl chlorides. The air- and moisture-stable catalysts are prepared in one step, and the coupling reactions proceed with a high selectivity for the benzyl position under mild conditions without the need for additives.