Mechanistic insights into the SN2-type reactivity of aryl-Co(iii) masked-carbenes for C–C bond forming transformations

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(sp2)–C(sp3) bond forming event to obtain...

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Bibliographic Details
Published in:Chemical science (Cambridge) 2018, Vol.9 (26), p.5736-5746
Main Authors: Planas, O, Roldán-Gómez, S, Martin-Diaconescu, V, Luis, J M, Company, A, Ribas, X
Format: Article
Language:English
Subjects:
Amides
Aromatic compounds
Carbenes
Forming
Reagents
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Summary: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(sp2)–C(sp3) 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 SN2-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.
ISSN:2041-6520
2041-6539
DOI:10.1039/c8sc00851e