SO₂F₂-Participated Oxidation Of Primary Amines And Reaction Of SO₂F₂ With 1,2-Diarylglycols

Sulfuryl fluoride（SO₂F₂）is a colorless and odorless gas that can stably exist up to 400℃i n dry environment.It has been used as a fumigant for more than 50 years.In 2014,professor Sharpless reported a new type of click reaction based on the Sulfur（VI）Fluroride Exchange（Su FEx）.Since then,sulfuryl fluoride,as one of the reactants of Su FEx reactions,has attracted significant attention to organic chemists.The click reaction based on Su FEx has brought chemists a powerful tool for research in the fields of protein labeling,material and medicine.Like perfluoroalkylsulfonyl fluoride,sulfuryl fluoride is also an excellent hydroxyl activating reagent,and can induce alcohols,carboxylic acid,aldoxime/ketoxime and phenols to undergo oxidation,substitution,rearrangement and cross-coupling reactions,and has been widely applied in organic synthesis.In the past decade,our research group has been focused on the project of“application of perfluoroalkylsulfonyl fluoride（R_fSO₂F）in organic synthesis”.Sulfuryl fluoride has similar chemical structure and properties to perfluoroalkylsulfonyl fluoride,but the two reagents differ in reactivity.Based on the previous works of our research group,this Master thesis aims to expand the application of sulfuryl fluoride in organic synthesis,and it mainly includes the following two parts:The first part:An efficient SO₂F₂/H₂O₂/base oxidation system developed by our research group was further subjected to the oxidation of aromatic amines and benzyl amines,and the corresponding azobenzene oxides and nitriles were respectively formed.The byproducts of these oxidation reactions resulting from the use of SO₂F₂/H₂O₂/base oxidation system are only water-soluble inorganic salts,and they can be easily removed through conventional work-up process.Therefore this method has potential application value in industrial manufacture.The second part:The reactions of sulfuryl fluoride with alcohols and phenols have been widely investigated,and the generated fluoride sulfonic acid ester compounds can be converted into a variety of products.However,the reaction of sulfuryl fluoride with vicinal diol compounds has not yet reported.In the second part of this thesis,we tested the reaction of sulfuryl fluoride with 1,2-diaryl glycols,and the results showed that unexpected ethylenyl fluorosulfontes were formed in medium to good yields.The unexpected products ethylenyl fluorosulfontes were then subsequently transformed into trisubstituted ethylene compounds through cross-coupling reaction,thus the application scope of SO₂F₂ was further broadened.