Cobalt-Nitrenoid Insertion-Mediated Amidative Carbon Rearrangement via Alkyl-Walking on Arenes

We herein disclose the Cp*Co(III)(LX)-catalyzed amidative alkyl migration using 2,6-disubstituted phenyl azidoformates. Upon the cobalt- nitrenoid insertion toward the substituted ortho carbon, an arenium cationic species bearing a quaternary carbon is generated, and a subsequent alkyl migration process is suggested to occur through an unforeseen alkyl-walking mechanism. A quinolinol ligand of the cobalt catalyst system is proposed to facilitate the final product-releasing rearomatization process by serving as an internal base. This new mechanistic mode enabled both [1,2]- and [1,4]-alkyl rearrangements to allow the structural variation of N-heterocyclic compounds.

Automated summary

In this study, a novel amidative alkyl migration reaction catalyzed by Cp*Co(III)(LX) using 2,6-disubstituted phenyl azidoformates as substrates was reported. The reaction mechanism involves an alkyl-walking process facilitated by a quinolinol ligand of the cobalt catalyst system, enabling both [1,2]- and [1,4]-alkyl rearrangements to allow structural variations of N-heterocyclic compounds.