Ammonia as Ultimate Amino Source in Synthesis of Primary Amines via Nickel-Promoted C-H Bond Amination.

The direct use of ammonia in transition-metal promoted C-H bond amination for the synthesis of primary amines is considered to be one of the major challenges in synthetic organic chemistry. Herein, we report that such transformation can be successfully achieved via nickel-promoted amination of inert arene C-H bonds with ammonia gas assisted by an 8-amino-quinoline directing group.

Selective Synthesis of Aryl Nitriles and 3-Imino-1-oxoisoindolines via Nickel-Promoted C(sp2)-H Cyanations.

An efficient nickel-promoted selective monocyanation of benzamides with TMSCN via 8-aminoquinoline directed ortho C-H activation has been developed. Varieties of functionalized ortho-cyanated (hetero)aryl nitriles can be selectively synthesized in moderate to good yields. These cyanation products can be easily transformed into various 3-imino-1-oxoisoindolines in a one-pot procedure. The mild reaction conditions, use of cheap and commercially available reagents, wide functional group tolerance, and operational convenience make this protocol practical to the synthetic community.