Difluoromethanesulfonyl hypervalent iodonium ylides for electrophilic difluoromethylthiolation reactions under copper catalysis.
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.
Department of Frontier Materials , Nagoya Institute of Technology , Gokiso, Showa-ku, Nagoya 466-8555 , Japan.
Sadayuki
S
Arimori
Department of Frontier Materials , Nagoya Institute of Technology , Gokiso, Showa-ku, Nagoya 466-8555 , Japan.
Okiya
O
Matsubara
Department of Frontier Materials , Nagoya Institute of Technology , Gokiso, Showa-ku, Nagoya 466-8555 , Japan.
Masahiro
M
Takada
Rigaku Corporation , 3-9-12 Matsubara-cho, Akishima, Tokyo 196-8666 , Japan.
Motoo
M
Shiro
Department of Frontier Materials , Nagoya Institute of Technology , Gokiso, Showa-ku, Nagoya 466-8555 , Japan.
Norio
N
Shibata
carbene; difluoromethylthiolation; fluorine; hypervalent iodonium ylide; sulfur