Visible Light Promoted Sulfonylation Of N-Alkyl-4-Piperidinols:Synthesis Of Homoallylic Sulfonamides

Homoallylamines compounds are a series of substances with important uses.Homoallylamines fragments are widely present in many natural products in nature.In particular,They are often used in medicinal chemistry and modern organic synthesis due to their special structure and high biological activity Medium.so the synthesis of Homoallylamines compounds was attracted much attention by scholars.There are some main synthetic methods of homoallylamines : nucleophilic addition of allyl reagents to C = N double bonds,transition metals catalyzed decarboxylative coupling reactions and tertiary amine rearrangements.Although homoallylamine compounds can be synthesized by these existing methods,some problems needed to be solved,such as,low atom economy,harsh reaction conditions,and use of expensive materials.Based on this,we committed to study the visible light promoted sulfonylation of N-alkyl-4-piperidinols for the synthesis of homoallylamine compounds under mild conditions.As a green energy source,visible light can be well used in organic synthetic applications because of their easy manipulation and mild reaction conditions.This thesis mainly explores a new methods for the synthesis of homoallylamine compounds via visible light promoted sulfonylation of N-alkyl-4-piperidinols.Subsequently,an aryl sulfinate compound was also effectively synthesized by the method promoted by visible light.Therefore,this paper is divided into three chapters in total.The main contents are as follows:The first chapter mainly introduces the application prospects,synthesis methods and research progress of homoallylamine compounds,highlights the principle of visible light-promoted reaction,and compares visible light-promoted synthesis reaction with various methods such as ordinary heating and electrochemistry.The advantages of these methods in synthetic application are discussed.The second chapter mainly discusses the visible light promoted sulfonylation of N-alkyl-4-piperidinols for the synthesis of N-homoallylsulfonamide.This method uses alizarin yellow R as a photocatalyst and visible light as the energy source.The reaction of N-alkyl-4-piperidinol and sulfonyl chloride to synthesize N-homoallyl sulfonamide compounds proceeded efficiently.The scope of the substrates of sulfonyl chloride andN-substituted piperidinol was screened.On the basis of ultraviolet spectroscopy and electron spin resonance EPR experiments,the possible reaction mechanism of visible light to promote the synthesis of N-homoallylsulfonamide was provided.The innovation of this synthesis method is to use visible light to promote the coupling reaction of sulfonyl chloride and N-alkyl-4-piperidinol,which has mild reaction conditions,good versatility of functional groups,high reactivity,good atom economy,and green Environmental protection.It is a very valuable new synthesis method of N-homoallylsulfonamide.The third chapter first introduces the application prospects and synthesis progress of sulfinate compounds,and then studies the specific scheme of visible light to promote the synthesis of aryl sulfinate.The sulfinate compound is an important compound,which plays an crucial role in the intermediates of medicinal chemistry and organic synthesis.The visible light-promoted aryl sulfinate synthesis scheme proposed in this paper is to use the charge transfer complex formed by aryl sulfonyl chloride and triethylamine to cleave and couple itself under room temperature visible light to obtain aryl sulfinate ester compounds.The method uses cheap and easily available sulfonyl chloride as a raw material,the reaction operation is simple,and the reaction is performed at room temperature under visible light,which has the advantages of low energy consumption and green environmental protection,and is a convenient and effective new method for sulfinate synthesis.