Metal-free Intermolecular Aminofluorination Of Styrene Derivatives

Fuorine substituted amino compounds are one kind of important organic compounds,because they have been widely applied in medicine and pesticide due to their significant biological and pharmacological activity.Accordingly,the synthesis of fuorine substituted amino compounds has attracted much attention.Aminofluorination reaction of olefins is one of the most simple and straightforward strategy access to fluorine substituted amino compounds.Transition-metal-catalyzed intramolecular aminofluorination of olefins has made great success and various important nitrogen heterocyclic compounds containing vicinal fluorine atom have been synthesized efficiently.However,intermolecular aminofluorination of olefins are rare.According to these reactions,transition metal are necessary,and the nitrogen source usually require to be pre-prepared.Therefore,the development of facile,efficient and metal-free intermolecular aminofluorination of olefins starting from readily available materials is of great significance.This thesis studied on metal-free intermolecular aminofluorination of styrene derivatives,mainly including two parts: One was that we have successlully realized intermolecular aminofluorination of styrene derivatives with Selectfluor as the oxidant and the fluorine source,triazole derivatives as the nitrogen source,various β-fluorine substituted benzylamine derivatives containing triazole skeleton were successfully synthesized under mild conditions.The other one was thedetailed research of the reaction mechanism,such as free radical inhibition experiments and mass spectrum experiment.All these results suggested that the styrene was firstly oxidized through single electron oxidation to form the cation radical intermediates,then following fluorine atom transfer,nucleophilic amination,obtained the fluorine substituted amino compounds with high selectivity finally.This thesis successfully realized metal-free three components intermolecular aminofluorination of styrene derivatives for the first time,and synthesized various high regioselectivity ortho fluorine substituted amine compounds with Selectfluor and triazole derivatives through single electron oxidation,fluorine atom transfer and nucleophilic amination process.The reaction conditions mild,simple operation,and with good functional group tolerance,the substrates are cheap and can get easily.This work demonstrates a new,simple,efficient and environmental benign approach for olefin bifunctional reaction.