Study On Photo-induced Reactions Enabled By EDA Complex Between Sodium Benzenesulfinate And Oxygen

Visible-light induced photochemistry is a remarkable green synthetic strategy because of its operational simplicity,high chemoselectivities and environmental friendliness,which has been widely employed in the fields of synthetic,pharmaceutical and functional material chemistry.In most cases,such reactions require the addition of extra catalysts or photosensitizers to realize the utilization of light energy,which in turn promotes subsequent chemical transformations.Recently,another visible light reaction model driven by based on the formation of complexes between electron-rich and electron-deficient compounds can avoid the addition of external catalysts,which is greener and environmentally friendly.Reversible ground-state photoactive charge transfer complexes through dipole-dipole interaction are formed by electron-rich and electron-deficient compounds,which are further converted into active radical intermediates to trigger the subsequent transformation under photoexcitation conditions,providing a new opportunity for synthetic chemistry.In this thesis,based on the formation of photoactive charge transfer complex between sodium benzenesulfinate and oxygen,conversion with different substrates has been achieved under visible light.The research work of this thesis is mainly divided into the following three parts:1)For the first time,it was found that sodium sulfinate could form a photoactive complex with oxygen.Under the excitation of light through a SET process,a sulfonyl radical was generated from the charge transfer complex,providing a powerful strategy for the sulfonylation.A series of highly functionalized CF₃-substituted tertiary alcohol compounds were successfully obtained by usingα-trifluoromethyl olefins as effective radical acceptors.In the presence of deuterium water,the deuterium at theα-position of the sulfonyl group is realized,which expands the application space of this reaction.2)Further research found that the catalytic amount of sulfonyl radicals could promote the addition of oxygen to olefins,thus forming dioxetane intermediates to subsequently aerobic oxidative cleavage of olefins.This method is suitable for both the simple alkenes,complex alkenes,alkenes substituted with halogen atoms,and complex drug molecules;producing the corresponding aldehydes,ketones,and halogen-transferred products respectively.3)Using the similar strategy,the method was applied to the oxidation of heteroatoms,green oxidation of hydrosilane was achieved.The chemical conversion of silanols to silyl ethers was realized in one-pot manner,which provided an efficient synthetic strategy for the preparation of various fatty silyl ethers.This new strategy has the characteristics of mild reaction conditions,simple operation and easy scale-up,which shows practical potential.