含氮杂环碱的双onic β，β -二甲基烯醇自由基阳离子的检测和跟踪反应( Detection and follow‐up reactions of distonic β,β‐dimesityl enol radical cations containing nitrogen heterocyclic bases )

ME Cinar M Lal Hans-Jörg Deiseroth J Schlirf M Schmittel cyclic voltammetry (CV density functional theory (DFT distonic radical cation, laser flash photolysis (LFP enol radical cation

β,β‐Dimesityl enols E2‐E4 containing various nitrogen heterocyclic bases in the α‐position were investigated by laser flash photolytic oxidation and density functional theory in order to identify distonic enol radical cations in solution and characterize their immediate follow‐up reactions. Enol E1 with a tert‐butyl group in the α‐position served as a reference. Experimental and computational efforts reveal that one‐electron oxidation of enol E1 furnishes the enol radical cation, whereas oxidation of E2‐E4 provides distonic radical cations in solution. While the distonic radical cations of E2‐E3 undergo intermolecular acid‐base reactions, the distonic radical cation of E4 experiences an intramolecular hydrogen ion followed by subsequent ring closure and ring‐opening steps. As a final product on the laser flash photolysis time scale, the rearranged radical cation E4d‐R is generated that is characterized by a dimesitylmethyl radical subunit.

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