Study On The Reaction Of TEA-3HF And Alkyne

Fluorine-containing compounds have been widely used in pharmaceuticals, paints, pesticides and materials because of their unique biological activity and physicochemical properties. Fluoroolefins and difluoromethylene fragment appeared in many structure of the drug. Due to the emergence of these special segments, the hydrophilic lipophilic, stability, metabolic rate of the organic molecules have been changed a lot. So research on the simple and highly effective method of fluorination methods has the vital significance.A new route to fluorovinyl acetates and β,β-difluoroacetate was developed via silver-catalyzed difunctionalization of terminal alkynes with PhI(OAc)2 and TEA·3HF. This novel one-pot process involving hydrofluorination and oxy or nitrogenation allows straightforward and efficient access to novel and biologically relevant structures. The optimum reaction conditions of fluorovinyl acetates are as follows:using 1.2 eq of PhI(OAc)2,2eq of TEA·3HF and 20 mol% Ag2CO3, in MeCN at 80℃ for 6 h, giving fluorovinyl acetates up in good yields and stereoselectivities (up to 95% yield and 99:1 Z/E). The optimum reaction conditions of β,β-difluoroacetate are as follows:using 1.2 eq of PhI(OAc)2,4 eq of TEA·3HF and 20 mol% Ag2CO3, in MeCN at 120℃ for 20 h, giving β,β-diffuoroacetate in 55%-77% yields.44 kinds compounds were synthesized and 35 of them were new compounds. The products were characterized by 1H NMR,13C NMR,19F NMR, HRMS, and XRD.