Exploring Superacid‐Promoted Skeletal Reorganization of Aliphatic Nitrogen‐Containing Compounds

Maxime Artault (1) , Thomas Cantin (1) , Mélissa Longuet (1) , Kassandra Vitse (1) , Christ Daniel Matatu Mbengo (1) , Frédéric Guégan (1, 2) , Bastien Michelet (1) , Agnès Martin‐mingot (1) , Sébastien Thibaudeau (1)

1 IC2MP [Poitiers] - Institut de chimie des milieux et matériaux de Poitiers [UMR 7285]
2 Université de Poitiers - Faculté de Sciences fondamentales et appliquées

Here we report a method to reorganize the core structure of aliphatic unsaturated nitrogen-containing substrates exploiting polyprotonation in superacid solutions. The superelectrophilic activation of N-isopropyl systems allows for the selective formal Csp3-H activation / cyclization or homologation / functionalization of nitrogen-containing substrates. This study also reveals that this skeletal reorganization can be controlled through protonation interplay. The mechanism of this process involves an original sequence of C–N bond cleavage, isopropyl cation generation and subsequent C–N bond and C–C bond formation. This was demonstrated through in situ NMR analysis and labelling experiments, also confirmed by DFT calculations.

Mots clés: Polycations; Rearrangement; Fluorine; Superacid; Heterocycles

Domaines: Chimie organique

Maxime Artault, Thomas Cantin, Mélissa Longuet, Kassandra Vitse, Christ Daniel Matatu Mbengo, et al.. Exploring Superacid‐Promoted Skeletal Reorganization of Aliphatic Nitrogen‐Containing Compounds. Angewandte Chemie International Edition, 2023, 63 (1), pp.e202316458. ⟨10.1002/anie.202316458⟩. ⟨hal-04520297⟩