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

Shulei Ge^1,2, Zhili Cui^1,2, Lei Peng^3,4, Xintong Wang⁵, Kaixin Chen^1,2, Changrui Nie^1,2, Shoucheng Dong^1,2, Yang Huang^3,4, Gen Luo(罗根)⁵*, Lin He(何林)^3,4*, Jie Li^1,2,6,7(李杰)*

¹State Key Laboratory of Bioinspired Interfacial Materials Science, Soochow University, Suzhou, China.

²College of Chemistry, Chemical Engineering and Materials Science, Soochow University, Suzhou, China.

³State Key Laboratory of Low Carbon Catalysis and Carbon Dioxide Utilization, Lanzhou Institute of Chemical Physics (LICP), Chinese Academy of Sciences, Lanzhou, China.

⁴State Key Laboratory for Oxo Synthesis and Selective Oxidation, Lanzhou Institute of Chemical Physics (LICP), Chinese Academy of Sciences, Lanzhou, China.

⁵Institutes of Physical Science and Information Technology, Anhui University, Hefei, China.

⁶Suzhou Key Laboratory of Pathogen Bioscience and Anti-infective Medicine, Soochow University, Suzhou, China.

⁷MOE Key Laboratory of Geriatric Diseases and Immunology, Soochow University, Suzhou, China.

Nat. Commun., 2025, 16, 8803.

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 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.

Article information: https://doi.org/10.1038/s41467-025-63875-4