Few methods have been reported for intermolecular arylamination of alkenes, which could provide direct access to important arylethylamine scaffolds. Herein, we report an intermolecular syn-1,2-arylamination of unactivated alkenes with arylboronic acids and O-benzoylhydroxylamine electrophiles with Ni(II) catalyst. The cleavable bidentate picolinamide directing group facilitates formation of stabilized 4-, 5- or 6-membered nickelacycles and enables the difunctionalization of diverse alkenyl amines with high levels of regio-, chemo- and diastereocontrol. This general and practical protocol is compatible with broad substrate scope and high functional group tolerance. The utility of this method is further demonstrated by the site-selective modification of pharmaceutical agents.

No abstract

Comprehensive Summary Directing group‐assisted, transition metal‐catalyzed three‐component difunctionalization of alkenes has emerged as a powerful tool to drive molecular complexity. However, this strategy generally works with the substrates bearing directing groups in close proximity to the alkene moieties, due to the preference for formation of kinetically stable five‐membered metallacycles. Herein, we have disclosed a complementary strategy to accomplish a nickel‐catalyzed remote arylalkylation of alkenyl amines with excellent regioselectivity and diastereofidelity, involving rare six‐ or seven‐membered metallacycles. This general protocol is compatible with a series of δ‐ and ε‐alkenyl amines, providing corresponding valuable δ,ε‐ and ε,ζ‐difunctionalized aliphatic amines that would be difficult to synthesize. The coordination of the bidentate picolinamide auxiliary and the facile oxidative addition of alkyl halides to Ni(I) species are the key to the success of the developed remote olefin dicarbofunctionalization.

An intermolecular syn-1,2-arylamination of unactivated alkenes with arylboronic acids and O-benzoylhydroxylamine electrophiles has been developed with Ni(II) catalyst. The cleavable bidentate picolinamide directing group facilitated formation of stabilized 4-, 5- or 6-membered nickelacycles and enabled the difunctionalization of diverse alkenyl amines with high levels of regio-, chemo- and diastereocontrol. This general and practical protocol was compatible with broad substrate scope and high functional group tolerance. The utility of this method was further demonstrated by the site-selective late-stage modification of pharmaceutical agents.

Copper‐catalyzed three‐component reactions of 2‐iodoanilines, benzylamines, and sulfur powder are reported to afford benzothiazoles in a simple one‐pot procedure by using water as solvent. A variety of 2‐arylbenzothiazoles were obtained in moderate to good yields up to 88%.