Rhodium-catalyzed Coupling Reaction Of Carbonyl-directed C-H Bonds With Vinyl Sulfonyl Fluoride

In recent years,with the rapid development of Sulfur(VI)Fluoride Exchange(Su FEx),Ethenesulfonyl Fluoride(ESF)and its derivatives have been used as high-efficiency linking molecules for sulfur-fluorine exchange reactions.With both alkenyl and sulfonyl fluoride(-SO2F)bifunctional potentials,it can be used as a new reagent to effectively introduce alkenyl or sulfonyl fluoride groups,and it can efficiently increase pharmacophores for simple organic compounds.Therefore,the related reactions and chemical transformations involved and mediated by vinylsulfonyl fluoride have important research significance and application value.At the same time,breakthroughs have been made in the field of transition metal-catalyzed organic chemistry over the past 30 years.Using a carbon-hydrogen(C-H)bond activation strategy,it is possible to start from simple organic compounds and directly construct carbon-carbon(C-C)bonds or carbon-hetero(C-X)bonds without the need for functional group conversion.This has great significance for the development of fields such as medicinal chemistry and materials science.In this article,we apply vinylsulfonyl fluoride to the field of transition metal-catalyzed organic chemistry.The introduction of vinyl sulfonyl fluoride or alkenyl functional group on vinyl sulfonyl fluoride realized into carbonyl-containing substrates successfully,completed the idea of direct CC bond construction guided by carbonyl groups,and realized the natural products and drugs derivative applications.2-Aryl(heterocyclic)substituted vinylsulfonyl fluoride has unique bifunctional electrophilic properties,which is an important component and research target of sulfur-fluorine exchange chemistry.In Chapter 2 of this paper,a novel coupling reaction between vinylsulfonyl fluoride and benzaldehyde or acetophenone catalyzed by a transition metal rhodium was successfully implemented to construct a novel2-aryl(heterocyclic)method for the substitution of vinylsulfonyl fluoride.This method has high universality and strong tolerance to various organic functional groups.In this chapter,41 novel 2-aryl(heterocyclic)substituted vinylsulfonyl fluorides with various structures were synthesized.At the same time,we have also applied this method to the modification of natural products and achieved good results.Alkenyl functional groups have various chemical transformation functions.At the same time,pyridine compounds are one of the most widely used chemical substances in the field of medicinal chemistry.Installing alkenyl functional groups on pyridine compounds can further realize the structural transformation of drugs and the development of new drugs.In Chapter 3 of this paper,the cyclic olefin insertion reaction of vinylsulfonyl fluoride and picolinamide derivatives catalyzed by the same transition metal rhodium was successfully constructed.This reaction synthesizes a variety of novel compounds with novel structures and potential biological activities containing pyridine rings and terminal olefins.This novel compound was also used as a raw material to achieve derivatization reactions involving a variety of terminal olefins.At the same time,the applicability of the method in pyridine drugs was tested and the practicality of the method was verified by gram-scale amplification experiments.The work in this paper further utilizes vinylsulfonyl fluoride in transition metal rhodium catalyzed reactions.Two types of compounds with novel structure and potential biological activity were synthesized,one was a new 2-aryl(heterocyclic)vinylsulfonyl fluoride substituted with an aldehyde ketone carbonyl group in the ortho position,and the other was a pyridine ring and a terminal new pyridopyrrole compounds of olefins,both of which are expected to be applied in the fields of medicinal chemistry,chemical biology,drug design and materials science.