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Activation of Trifluoromethylthio Moiety by Appending Iodonium Ylide under Copper Catalysis for Electrophilic Trifluoromethylation Reaction
Author(s) -
Saidalimu Ibrayim,
Suzuki Shugo,
Tokunaga Etsuko,
Shibata Norio
Publication year - 2016
Publication title -
chinese journal of chemistry
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 1.28
H-Index - 41
eISSN - 1614-7065
pISSN - 1001-604X
DOI - 10.1002/cjoc.201600029
Subject(s) - trifluoromethylation , chemistry , ylide , electrophile , nucleophile , reagent , trifluoromethyl , moiety , medicinal chemistry , intramolecular force , sulfonium , catalysis , organic chemistry , combinatorial chemistry , alkyl , salt (chemistry)
A novel iodonium‐ylide compound 2 that appends atrifluoromethylthio (SCF 3 ) group is disclosed as a new, shelf‐stable electrophilic trifluoromethylation reagent. Unlike known shelf‐stable electrophilic trifluoromethylation reagents, 2 has a stable SCF 3 group which is activated by appending iodonium ylide under copper catalysis via sulfonium ylide to generate a cationic trifluoromethyl (CF 3 ) species. Reagent 2 was found to be an efficient electrophilic trifluoromethylation reagent for a wide range of silyl enol ethers 3 under copper catalysis. Cyclic and acyclic α ‐trifluoromethyl ketones 4 were obtained by reagent 2 in moderate to good yields. On the other hand, a difluoromethylthio analogue 5 did not affect intermolecular transfer difluoromethylation to substrates. Instead, intramolecular 1,4‐migration proceeded similar to the Stevens rearrangement to provide 6 in 21% yield, independent of the presence of nucleophiles 3 .