C-C Bond Breaking in Addition-Elimination Reactions on Nitriles

Jean-Marc Mattalia (1) , Paola Nava (1)

1 ISM2 - Institut des Sciences Moléculaires de Marseille

The nucleophilic addition of organometallics to nitriles leads to an imine‐type intermediate. When the α‐position is substituted with a carbanion stabilizing group, an elimination can follow, resulting in a C–C bond breaking. This paper proposes a computational study of this step. Starting from the transnitrilation reaction by DMMN (dimethylmalononitrile), a comparison of several methods shows that the PBE0‐D3 level is suitable for this study. The imine adducts display particularly stretched C–C bond and thus the computed barriers are low. Both electronic and steric effects influence the leaving group ability as well as its interaction with the metal.

Domaines: Chimie organique

Jean-Marc Mattalia, Paola Nava. C-C Bond Breaking in Addition-Elimination Reactions on Nitriles. European Journal of Organic Chemistry, 2019, 2019 (15), pp.2621-2628. ⟨10.1002/ejoc.201900119⟩. ⟨hal-02125621⟩