Organic chemistry

Diazo

Wolff rearrangement

Stereochemistry

Density functional theory

Catalysis

Computational chemistry

Medicinal chemistry

Chemistry

Ketene

Alkyl

Aryl

Cobalt

Photochemistry

ACS Catalysis

An unusual cobalt(III)-catalyzed cross-coupling/cyclization of aryl C–H bonds of N-nitrosoanilines with α-diazo-β-ketoesters has been achieved. This protocol features a unique combination of Csp2-H activation/Wolff rearrangement process, allowing for the rapid assembly of quaternary 2-oxindoles. The empirical evidence and density functional theory (DFT) calculations reveal the trapping process of transient acceptor ketene intermediates by cobalt metallocycles.

Co(III)-Catalyzed Coupling-Cyclization of Aryl C–H Bonds with α-Diazoketones Involving Wolff Rearrangement