Abstract
Herein we describe the synthesis and characterization of a family of C-metalated aryl-Co(iii) enolates, which can be considered as masked-carbenes, using diazoacetates as coupling partners. These species have been proved to be necessary intermediates in the C(sp(2))-C(sp(3)) bond forming event to obtain cyclic amides, taming the elusive Co(iii)-carbene species. The scope of diazoacetates has been exhaustively examined, varying the nature of the ester and the α-substitution, and a clear preference for electron-poor carbene precursors is observed. Exhaustive experimental and theoretical studies indicate that an unprecedented intramolecular S(N)2-type process governs the formation of the newly formed C-C bond. Furthermore, the key role of several Lewis acids as carboxylate-activating reagents is further explored by DFT calculations.