3 years ago

C−N Bond Activation and Ring Opening of a Saturated N-Heterocyclic Carbene by Lateral Alkali-Metal-Mediated Metalation

C−N Bond Activation and Ring Opening of a Saturated N-Heterocyclic Carbene by Lateral Alkali-Metal-Mediated Metalation
Alan R. Kennedy, Alberto Hernán-Gómez, Eva Hevia
Combining alkali-metal-mediated metalation (AMMM) and N-heterocyclic carbene (NHC) chemistry, a novel C−N bond activation and ring-opening process is described for these increasingly important NHC molecules, which are generally considered robust ancillary ligands. Here, mechanistic investigations on reactions of saturated NHC SIMes (SIMes=[:C{N(2,4,6-Me3C6H2)CH2}2]) with Group 1 alkyl bases suggest this destructive process is triggered by lateral metalation of the carbene. Exploiting co-complexation and trans-metal-trapping strategies with lower polarity organometallic reagents (Mg(CH2SiMe3)2 and Al(TMP)iBu2), key intermediates in this process have been isolated and structurally defined. Co-lateral damage! Lateral metalation of saturated N-heterocyclic carbene [:C{N(2,4,6-Me3C6H2)CH2}2] (SIMes) triggers a destructive process, inducing C−N bond activation and ring opening of the five-membered heterocyclic ring.

Publisher URL: http://onlinelibrary.wiley.com/resolve/doi

DOI: 10.1002/anie.201702246

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