Stable dicationic dioxoliums and fate of their dioxolyl radicals

Marc Devillard (1) , Vianney Regnier (2) , Jacques Pécaut (3, 4) , David Martin (2)

1 LHFA - Laboratoire Hétérochimie Fondamentale et Appliquée
2 DCM - CIRE - Département de Chimie Moléculaire - Chimie Inorganique Redox
3 CIBEST - Chimie Interface Biologie pour l’Environnement, la Santé et la Toxicologie
4 DIESE - Département Interfaces pour l'énergie, la Santé et l'Environnement

Stable dicationic dioxolium salts featuring an ancillary vinamidinium pattern were synthesized and characterized. Although highly reactive, they were found otherwise easy to handle under inert atmosphere. This offered the opportunity to generate and study the fate of unknown 1,3-dioxolyl radicals. Depending on substituents, reduction led to the formation of dimers of either dioxolyl or cyclohexadienyl radicals, stemming from a process that is related to the Surzur-Tanner rearrangement. The cyclohexadienyl radical could be characterized in the case of a tri(tert-butyl)phenyl group, which prevents dimerization processes.

Domaines: Chimie organique

Marc Devillard, Vianney Regnier, Jacques Pécaut, David Martin. Stable dicationic dioxoliums and fate of their dioxolyl radicals. Organic Chemistry Frontiers, 2019, 6 (18), pp.3184-3191. ⟨10.1039/C9QO00298G⟩. ⟨hal-02094850⟩