Studies On The Coupling Reactions Based On Sulfur Fluoride Exchange (SuFEx)

Sulfur Fluoride Exchange(Su FEx)is a new generation of click chemistry,which takes advantage of the special stability of the S-F bond and its reactivity of nucleophilic substitution under specific conditions.It has a great application prospect in material chemistry,pharmaceutical chemistry and biochemistry.Ethenesulfonyl fluoride(ESF)and sulfuryl fluoride(SO₂F₂)are important S-F connective molecules,it will be of great theoretical and practical significance to explore their applications in Su FEx chemistry and other organic transformations.This dissertation starts with these two important S-F connective molecules,ESF and SO₂F₂,developing novel methods for the synthesis of new S-F molecules,exploring the new reaction properties of ESF and SO₂F₂,and expanding the theoretical scope of Su FEx chemistry.The main research contents are listed as follows:1.As derivatives of ESF,2-arylethenesulfonyl fluorides represent a rare family of selectively addressable bifunctional electrophiles and can be a new scaffold of Su FEx chemistry.An oxidative coupling of N-methoxybenzamides and ESF via Rhodium(III)-catalyzed ortho-C-H activation was described.The strategy of C-H bonds functionalization provided twenty-two 2-arylethenesulfonyl fluorides,three sulfonyl fluoride substituted lactones and thirteen?-lactams.This protocol featured in excellent regioselectivity and functional group tolerance.The activity of ESF in C-H bonds functionalization relative to other commonly used coupling reagents was also evaluated.This method provided a new route for the synthesis of 2-arylethenesulfonyl fluorides and expanded the application range of ESF.2.A Rh(III)-catalyzed activation of ortho-C-H bonds of arylcarboxylic esters for monoselective coupling with ESF was developed.This protocol provided a convenient procedure to synthesize twenty-seven examples of otherwise difficult to access 2-arylethenesulfonyl fluorides possessing ortho-carboxylic esters functionality.It provided a material basis for the introduction of 2-arylethenesulfonyl fluoride into the biological system.At the same time,the antibacterial activities of eighty-two2-arylethenesulfonyl fluoride compounds were investigated,which laid a foundation for the biological activities and pharmacological studies of 2-arylethenesulfonyl fluoride compounds.3.The new reactivity of SO₂F₂ as carboxylic acids activation agent was developed and applied into amidation and esterification reactions.The SO₂F₂mediated direct coupling of carboxylic acids with amines was developed for the synthesis of a broad scope of amides and dipeptides in a simple,mild,efficient,robust and practical manner.The SO₂F₂ mediated direct coupling of carboxylic acids with alcohols was deveploped for the synthesis of a broad scope of esters with mild conditions,high-efficiency and steric hindrance tolerance.The SO₂F₂ mediated coupling reactions of carboxylic acids with amines and alcohols demonstrated the novel reactivity of SO₂F₂ and provided a simple,feasible and industry applicable methods for the synthesis of amides and esters.