Pincer-cobalt boosts divergent alkene carbonylation under tandem electro-thermo-catalysis.

Catalytic multicomponent carbonylation reactions with high regio- and chemoselectivity represent one of the long-pursued goals in C1 chemistry. We herein disclose a practical cobalt-catalyzed divergent radical alkene carbonylative functionalization under 1 atm of CO at 23 °C. The leverage of the tridentate NNN-type pincer ligand is the key to avoid the formation of catalytically inert Co0(CO)n species and overcome the occurrence of oxidative carbonylation of organozincs, selectively tuning the catalytic reactivity of cobalt center for dictating a full cobalt-catalyzed four-component carbonylation. Moreover, direct use CO2 as the C1 source in the multicomponent alkene carbonylative couplings can be achieved under a tandem electro-thermo-catalysis, thus allowing us to rapidly and reliably construct unsymmetric ketones with ample scope and excellent functional group compatibility. Remarkably, our protocol encompasses a broader of polyhaloalkanes as the electrophiles, which underwent radical-relay couplings in a completely regio- and chemoselective fashion. Finally, facile modifications of drug-like molecules demonstrate the synthetic utility of this method.