Ethenesulfonyl Fluoride: The Most Perfect Michael Acceptor Ever Found?

• Published in: Angewandte Chemie International Edition Vol. 55; no. 41; pp. 12664 - 12667
• Main Authors: Chen, Quan, Mayer, Peter, Mayr, Herbert
• Format: Journal Article
• Language: English
• Published: WEINHEIM Blackwell Publishing Ltd 04.10.2016; Wiley; Wiley Subscription Services, Inc
• Edition: International ed. in English
• Subjects: Aromatic compounds; Chemistry; Chemistry, Multidisciplinary; electrophilic aromatic substitution; electrophilicity; Fluorides; linear free-energy relationships; Nucleophiles; Photometry; Physical Sciences; Pyridinium; Pyrroles; Reaction kinetics; Science & Technology; ylides; ylides; SULFUR YLIDES; SCOPE; CYCLOPROPANATION; COMBINATIONS; reaction kinetics; CHEMISTRY; NUCLEOPHILIC REACTIVITIES; ELECTROPHILICITIES; electrophilic aromatic substitution; POLAR ORGANIC-REACTIVITY; electrophilicity; linear free-energy relationships
• ISSN: 1433-7851; 1521-3773; 1521-3773
• DOI: 10.1002/anie.201601875

The kinetics of the reactions of ethenesulfonyl fluoride (ESF) with sulfonium and pyridinium ylides were measured photometrically to determine the electrophilicity parameter of ESF according to the correlation lg k20 °C=sN(N+E). With E=−12.09, ESF is among the strongest Michael acceptors in our comprehensive electrophilicity scale, which explains its excellent performance in reactions with many nucleophiles. Its predicted usability as a reagent in electrophilic aromatic substitutions with electron‐rich arenes was confirmed by uncatalyzed reactions with alkyl‐substituted pyrroles. Kinetic studies of the reactions of ethenesulfonyl fluoride and styrenesulfonyl fluoride with sulfonium and pyridinium ylides reveal that the SO2F group activates C=C bonds 106 to 108 times more strongly towards nucleophilic attack than an SO2Ph or SO2Tol group. Ethenesulfonyl fluoride is thus one of the most electrophilic monosubstituted ethylenes ever reported (compare the electrophilicity parameters E).