Regioselective nickel-catalyzed dicarbofunctionalization of unactivated alkenes enabled by picolinamide auxiliary

Catalytic difunctionalization of alkenes has been a prominent research theme in recent years. Here, we develop a removable bidentate picolinamide-assisted regioselective dicarbofunctionalization of homoallylic amines with organohalides and arylboronic acids. The catalytic system, using cost-effective and air-stable Ni(II) precatalyst, which could be activated by arylboronic acids, provides access to the regioselective diarylation and arylalkylation of unactivated alkenes. This reaction is compatible with alpha- or beta-substituted terminal alkenes and internal alkenes and exhibits excellent functional group and heterocycle tolerance. Preliminary mechanistic studies suggest that the reaction proceeds via a Ni-I/Ni-III catalytic cycle rather than a Ni-0/Ni-II cycle. Notably, the general and practical protocol developed herein represents, to the best of our knowledge, the first example of Ni-catalyzed 3-component 2, 1-diarylation and arylalkylation of alkenes with arylboronic acids and organohalides.

Automated summary

The research presented here developed a novel catalytic system for regioselective dicarbofunctionalization of homoallylic amines. By activating cost-effective Ni(II) precatalyst with arylboronic acids, selective diarylation and arylalkylation of unactivated alkenes was achieved.