Copper-Catalyzed Fluoroalkyl And Azide Modification Of Olefins

Nitrogen is an element that is abundant in the earth.Many natural products and synthetic compounds contain nitrogen.N-heterocyclic compounds containing nitrogen atoms are key skeletor for some functional materials and pharmaceutical compounds,e.g.COX-2 inhibitors（celecoxib）,atorvastatin calcium,and rizatriptan.Therefore,it has always been a research hotspot and a difficult research filed for scientists to introduce a nitrogen-confained moiefy into an organic compound.Methods for constructing C-N bonds typically include substitution reactions（electrophilic and nucleophilic amination）,cycloadditions,condensations,rearrangements,and cross-couplings,et.al.Fluorine has very property special.Fluorine compounds play important roles in the fields of agrochemistry,medicinal chemistry,and materials science.The introductions of fluorine atom and fluoroalkyl gruops into organic compounds can increase their solubility,lipophilicity,bioavailability,and metabolic stability.In the case of the introductions of fluorine into medicines and pesticides can greatly change the efficacy of pharmaceuticals and pesticide molecules.Therefore,chemists are trying to establish new and efficient methods for introducing fluorine into organic compounds.The difunctionalization of olefins is a very highly way for introducing functional groups into organic compounds.Due to the difunctionalization of olefins can introduce two functional groups at the same time,a dual change in the structure of alkenes can be achieved.In recent years,the use of difunctionalization of olefins to achieve the one-step introduction of nitrogen and fluoalkyl group into compounds has been a hot topic in organic synthesis,especially in the field of drug discovery.With the continuous effort in the organic systhesis,scientists are no longer limited to the use of heat to provide energy for the reaction,and began to pay attention to other forms of energy,such as:light,electricity and so on.With this idea in mind,this paper achieved the first example of photo-induced,Cu-catalyzed azido fluoroalkylation of olefins.Cu（MeCN）₄PF₆ was used as the catalyst,fluoroalkyl iodide was used as the fluorine source,and TMSN₃ was used as the nitrogen source.In the reaction,UV light was used to promote the oxidative quenching of Cu catalysts.Without the help of expensive Ru or Ir photocatalysts,CF₃I/R_f I smoothly reduced to·CF₃/·R_f and I^-.The rapid conversion of CF₃I/R_fI to I^-and in situ generated amine radical cations successfully inhibits the competing two-component fluoroiodoalkylation side reactions and promotes the required three-component reactions.The reactions were effective for introducing both-R_f and-CF₃ under irradiation of a25-W UVC fluorescent lamp at room temperature.