Difluoromethanesulfonyl hypervalent iodonium ylides 2 were developed as electrophilic difluoromethylthiolation reagents for a wide range of nucleophiles. Enamines, indoles, β-keto esters, silyl enol ethers and pyrroles were effectively reacted with 2 affording desired difluoromethylthio (SCF2H)-substituted compounds in good to high yields under copper catalysis. The reaction of allyl alcohols with 2 under the same conditions provided difluoromethylsulfinyl (S(O)CF2H) products in good yields. The difluoromethylthiolation of enamines is particularly effective with wide generality, thus the enamine method was nicely extended to the synthesis of a series of difluoromethythiolated cyclic and acyclic β-keto esters, 1,3-diketones, pyrazole and pyrimidine derivatives by a consecutive, two-step one-pot reaction using 2.
Electrophilic trifluoromethylthiolation of allylsilanes and silyl enol ethers with trifluoromethanesulfonyl hypervalent iodonium ylide has been conducted. In the presence of a catalytic amount of CuF2, the reaction proceeded in modest to high yields under mild conditions.
Trifluoromethylsulfinyl and trifluoromethylthio groups are both important substituents for pharmaceuticals, agrochemicals and functional materials. We herein report the trifluoromethylthiolation of allyl alcohols 2 with trifluoromethanesulfonyl hypervalent iodonium ylide 1 under copper catalysis to provide trifluoromethylsulfinyl compounds 3. Trifluoromethylthiolation of boronic acids 4 with 1 furnished trifluoromethylthio compounds 5.
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