Open AccessOlefination with Sulfonyl Halides and Esters: Synthesis of Unsaturated Sulfonyl Fluorides
Author(s) -
Michał Tryniszewski,
Dariusz Basiak,
Michał Barbasiewicz
Publication year - 2022
Publication title -
organic letters
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 1.94
H-Index - 239
eISSN - 1523-7060
pISSN - 1523-7052
DOI - 10.1021/acs.orglett.2c01604
Subject(s) - chemistry , sulfonyl , carbanion , knoevenagel condensation , adduct , fluoride , medicinal chemistry , pyridine , halide , organic chemistry , catalysis , inorganic chemistry , alkyl
Methanedisulfonyl fluoride, CH 2 (SO 2 F) 2 , transforms aromatic aldehydes into β-arylethenesulfonyl fluorides, useful substrates for the SuFEx "click"-type transformations. The reaction mimics mechanism of the Horner-Wadsworth-Emmons olefination, which runs via addition of the carbanion, followed by cyclization-fragmentation of the four-membered ring intermediate. In the absence of base, electron-rich aldehydes follow an alternative pathway of the Knoevenagel condensation to provide unsaturated 1,1-disulfonyl fluorides. We demonstrate also trapping of elusive ethene-1,1-disulfonyl fluoride, CH 2 ═C(SO 2 F) 2 , with 4-(dimethylamino)pyridine (DMAP) that forms zwitterionic adduct, characterized with X-ray studies.