Recent developments in nickel-catalyzed intermolecular dicarbofunctionalization of alkenes

Abstract

Nickel-catalyzed three-component alkene difunctionalization has rapidly emerged as a powerful tool for forging two C-C bonds in a single reaction. Building upon the powerful modes of bond construction in traditional two-component cross-coupling, various research groups have demonstrated the versatility of nickel in enabling catalytic 1,2-dicarbofunctionalization using a wide range of carbon-based electrophiles and nucleophiles and in a fully intermolecular fashion. Though this area has emerged only recently, the last few years have witnessed a proliferation of publications on this topic, underscoring the potential of this strategy to develop into a general platform that offers high regio- and stereoselectivity. This minireview highlights the recent progress in the area of intermolecular 1,2-dicarbofunctionalization of alkenes via nickel catalysis and discusses lingering challenges within this reactivity paradigm.

Scheme 1. General scheme depicting nickel-catalyzed intermolecular 1,2-dicarbofunctionalization of alkenes.

Scheme 2. Organization of topics in this review based on alkene substrate and stabilization strategy.

Fig. 1. 1,2-Dicarbofunctionalization of benzyl acrylate using phenyl zinc chloride and RAEs.

Fig. 2. (A) Reductive 1,2-dicarbofunctionalization of acrylate-type compounds. (B) Proposed catalytic cycle.

Fig. 3. 1,2-Difluoroalkylarylation of enamides.

Fig. 4. (A) Asymmetric 1,2-dicarbofunctionalization of vinyl-Bpin. (B) Proposed mechanism.

Fig. 5. 1,2-Diarylation of styrenyl aldimines.

Fig. 6. 1,2-Dicarbofunctionalization of alkenyl arenes reported by (A) Giri and coworkers and (B) Brown and coworkers.

Fig. 7. (A) Asymmetric reductive 1,2-homodiarylation of vinyl arenes. (B) Key mechanistic experiment and proposed catalytic cycle.

Fig. 8. 1,2-Carboacylation of norbornenes.

Fig. 9. (A) Directed 1,2-arylalkylation of β,γ-unsaturated alkenyl carbonyl compounds. (B) Key mechanistic experiment and proposed catalytic cycle.

Fig. 10. Directed 1,2-dialkylation of β,γ- and γ,δ-unsaturated alkenyl carbonyl compounds.

Fig. 11. Divergent regioselectivity in 1,2-dicarbofunctionalization of allyl amines using pyrimidine directing groups.

Fig. 12. (A and B) Imine-directed 1,3- and 1,2-diarylation of γ,δ-unsaturated ketimines. (C) 1,3-Vinylarylation of γ,δ-unsaturated α-cyanoesters.

Fig. 13. (A) Reductive 1,2-perfluoroalkylacylation of allylic substrates. (B) Proposed catalytic cycle.

Fig. 14. Simple amide-directed 1,2-diarylation.

Fig. 15. 1,2-Allylmethylation of N-allyl heterocycles.

Fig. 16. 1,2-Diarylation of β,γ-unsaturated alkenyl carboxylic acids and synthetic applications.

Fig. 17. Photocatalytic 1,2-arylalkylation of alkenes reported by (A) Chu and coworkers and (B) Nevado and coworkers.