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

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Superacid Chemistry Protonation Isopropyl Nitrogen Bond cleavage Surface modification Reaction mechanism Stereochemistry Organic chemistry Catalysis Physical chemistry Ion

Maxime Artault , Thomas Cantin , Mélissa Longuet , Kassandra Vitse , Christ Daniel Matatu Mbengo , Frédéric Guégan , Bastien Michelet , Agnès Martin‐Mingot , Sébastien Thibaudeau ·

YOU? · · 2023 · Open Access · · DOI: https://doi.org/10.1002/ange.202316458 · OA: W4388863110

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 C sp3 −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.