In the past decade, Co(II)-based metalloradical catalysis (Co(II)-MRC) has been successfully applied to enantioselective constructions of various chiral building blocks. With the use of cobalt(II) complex of porphyrin as stable 15e-metalloradical, it can homolytically activate diazo compounds (termed as metalloradicophiles) to generate the corresponding α-Co(III)-alkyl radicals which are involved in the subsequent intermolecular or intramolecular radical addition (RA) or hydrogen atom abstraction (HAA) reactions. Finally, radical substitution (RS) to deliver the corresponding products. Our continued efforts on developing new transformations with Co(II)-MRC have broaden its synthetic application. The key factor to the success is the design and synthesis of effective metalloradical catalyst. Detailed experimental and computational studies help to disclose the underlying stepwise radical reaction mechanism.

Enantioselective transformations with diazo compounds via Co(II)-based metalloradical catalysis

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