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Novel Bifunctionalization of Activated Methylene: Base‐Promoted Trifluoromethylthiolation of β‐Diketones with Trifluoromethanesulfinyl Chloride
Author(s) -
Sun DongWei,
Jiang Min,
Liu JinTao
Publication year - 2019
Publication title -
chemistry – a european journal
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 1.687
H-Index - 242
eISSN - 1521-3765
pISSN - 0947-6539
DOI - 10.1002/chem.201901781
Subject(s) - methylene , chemistry , substituent , chloride , base (topology) , intramolecular force , medicinal chemistry , organic chemistry , mathematics , mathematical analysis
A novel bifunctionalization of activated methylene was achieved successfully through the base‐promoted trifluoromethylthiolation of β‐diketones or β‐ketoesters with trifluoromethanesulfinyl chloride. A series of α‐trifluoromethylthiolated α‐chloro‐β‐diketones and α‐chloro‐β‐ketoesters were obtained in moderate to good yields under mild conditions. When β‐diketones containing a phenyl group with a hydroxyl or amino substituent at the ortho position were used as substrates, intramolecular trifluoromethylthiolation/cyclization reaction took place to give the corresponding cyclic products. Furthermore, the protocol could be extended to perfluoroalkylthiolation with the sodium perfluoroalkanesulfinate/POCl 3 system. On the basis of experimental results, plausible mechanisms are proposed.