Regio- and stereoselective synthesis of tetrasubstituted (E)-(2-chloro-2-fluoro-1-iodovinyl)dimethylphenylsilane and its desilylative sonogashira coupling.

Trihalo-substituted vinylsilane was readily synthesized in 77% yield and in an excellent regio- and stereoselective manner from in situ-generated fluorosilylacetylene, followed by the addition of I2 and NCS. The silane was committed to sequential Sonogashira coupling with various terminal acetylenes under mild conditions, affording desilylated chlorofluoro-enyne adducts in moderate to good yields.

Property and reactivity of fluoro(silyl)acetylenes and fluoro(stannyl)acetylenes.

Fluoro(silyl)acetylenes and fluoro(stannyl)acetylenes underwent a radical addition reaction of THF to furnish the corresponding fluorinated cyclic ethers in moderate to good yields. These intriguing addition reaction proved to proceed via a radical reaction mechanism.

Preparation and reactions of (beta-trifluoromethyl)vinyl sulfonium salt.

(Beta-trifluoromethyl)vinyl sulfonium salt as a novel three-carbon fluorinated building block was conveniently prepared from easily available (beta-trifluoromethyl)vinyl sulfide and diphenyl iodonium salt in excellent yield. This easily handled crystalline reagent displayed two types of useful transformation involving aziridination and vinylation to afford the corresponding trifluoromethylated compounds in excellent yields.