1. Exploring Superacid‐Promoted Skeletal Reorganization of Aliphatic Nitrogen‐Containing Compounds.
- Author
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Artault, Maxime, Cantin, Thomas, Longuet, Mélissa, Vitse, Kassandra, Mbengo, Christ Daniel Matatu, Guégan, Frédéric, Michelet, Bastien, Martin‐Mingot, Agnès, and Thibaudeau, Sébastien
- Subjects
ALIPHATIC compounds ,SCISSION (Chemistry) ,RING formation (Chemistry) - Abstract
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. [ABSTRACT FROM AUTHOR]
- Published
- 2024
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