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

Ge, Shulei; Cui, Zhili; Peng, Lei; Wang, Xintong; Chen, Kaixin; Nie, Changrui; Dong, Shoucheng; Huang, Yang et al. · Nat Commun · 2025

basic_science · Level V

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Abstract

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 Co<sup>0</sup>(CO)<sub>n</sub> 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 CO<sub>2</sub> 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.