Studies On The Synthesis Of Fluorine-Containing Organic Compounds Under Transition Metals Catalysis Based On Reductive Coupling Reaction

Fluorine is an element with unique properties.The introduction of a fluorine atom or fluoroalkyl group into molecules,due to the unique properties of fluorine,has become a powerful and widely used strategy in the fields of pharmaceuticals,agrochemicals and functional materials since it often produces great variation in chemical and physical properties.Recently,transition-metal-catalyzed fluoroalkylation reaction has received widespread attention and development.On the basis of previous research,we realized various strategies to obtain fluorinated molecules,using cheap fluorine-containing industrial raw materials as fluorine sources via transition-metal-catalyzed reductive coupling reaction.Ⅰ:Nickel-catalyzed aryl-difluoroacetylation of N-vinylacetamideIn this part,a nickel-catalyzed reductive aryldifluoroacetylation of N-vinylacetamide with ethyl chloro(difluoro)acetate and aryl iodides is described.This chelating amide carbonyl group-assisted strategy provides rapid access to a variety of protected α,α-difluoro-β-amino acids that might have potential applications in peptide chemistry and protein engineering.An advantage of this method is its synthetic simplicity,avoiding preparation of organometallic reagents.Ⅱ:Cobalt-catalyzed 3,3,3-trifluoropropenylation of aryl bromideIn this part,we have developed a cobalt-catalyzed reductive coupling reaction of(E)-1-Chloro-3,3,3-trifluoroprop-l-ene(HCFO-1233zd(E))with aryl bromide.HCFO-1233zd(E)is a cheapful,commercial available compound,which is used as efficient refrigerant and foamer.In this reaction,HCFO-1233zd(E)was reacted with aryl bromide and the corresponding products was obtained via cobalt-catalyzed reductive coupling reaction under mild conditions.This reaction exhibits high functional group tolerance and a broad substrate scope.Meanwhile,the resulting fluorinated alkenes can serve as versatile building blocks for the various transformations.