Nickel-Catalyzed Ipso/Ortho Difunctionalization of Aryl Bromides with Alkynes and Alkyl Bromides via a Vinyl-to-Aryl 1,4-Hydride Shift

Abstract

Polysubstituted arenes are ubiquitous structures in a myriad of medicinal agents and complex molecules. Herein, we report a new catalytic blueprint that merges the modularity of nickel catalysis for bond formation with the ability to enable a rather elusive 1,4-hydride shift at arene sp2 C–H sites, thus allowing access to ipso/ortho-difunctionalized arenes from readily available aryl halides under mild conditions and exquisite selectivity profile.

Nickel catalyzed multicomponent stereodivergent synthesis of olefins enabled by electrochemistry, photocatalysis and photo-electrochemistry

“…Our initial results showed that traditional reductants such as Mn 51 , Zn, Mg, and TDAE 52 were inefficient in this three-component cross-electrophile coupling, affording low or no yield of the desired product. Photocatalysts including [Ir(dFCF 3 ppy) 2 dtbbpy]PF 6 , Ru(bpy) 3 (PF 6 ) 2 , 4CzIPN and Eosin Y all showed low catalytic reactivity or generated products with poor stereoselectivity (Fig.…”

Nickel-catalyzed hydroarylation reaction: a useful tool in organic synthesis

“…Several core structures of bioactive and pharmacological compounds, including L-menthol, glucose, empagliflozin, and canagliflozin, may be easily introduced in Scheme 27 Nickel-catalyzed ipso/ortho difunctionalization of aryl bromides. 47 Scheme 29 NiH-catalyzed enantio and regioselective reductive hydroarylation. 49 Scheme 28 Nickel-catalyzed hydroarylation reaction of alkene.…”

“…NaI under N , N -dimethylacetamide solvent at room temperature for 24 h, which afforded the desired product 45 in 51–82% yield (Scheme 27). 47 Esters, amides, sulphonamides, phosphonates, amines, nitriles, sulfones, and ketones groups were employed in this reaction very well. Electron-donating arene substituents, ortho -substituted arenes, and heterocyclic motifs also underwent this reaction very well.…”

Synergism of Fe/Ti Enabled Regioselective Arene Difunctionalization

“…Aryne chemistry plays an important role in this area and allows for a Nu/E-type ODF by addition with a nucleophile and subsequent trap with an electrophilic (Scheme A) . Recently, ODFs promoted by Pd/norbornene combinations, known as Catellani-type reactions, have been extensively studied, and great progress has been made (Scheme A) . 1,2-Bimetallic arylene reagents can be an alternative tool for ODF, which could accomplish E/E(′)-type difunctionalization through two electrophilic reactions (Scheme B).…”