Photoinduced Nickel-Catalyzed Deaminative Cross-Electrophile Coupling

The construction of carbon-carbon bonds through cross-coupling between two electrophiles in the absence of excess metallic reducing agents is a desirable objective in chemistry. Here, we show that N-alkylpyridinium salts can be efficiently merged with aryl or alkyl halides in an intermolecular fashion, affording products in up to 90%

yield at ambient temperature. These reactions harness the ability of N-alkylpyridinium salts to form electron donor-acceptor complexes with Hantzsch esters, enabling photoinduced single-electron transfer and fragmentation to afford alkyl radicals that are subsequently trapped by a Ni-based catalytic species to promote C(sp²)-C(sp³) and

C(sp³)-C(sp³) bond formation. The operationally simple protocol is applicable to site-selective cross-coupling and tolerates diverse functional groups, including those that are sensitive towards metal reductants.