A Heck–Matsuda Process for the Synthesis of β‐Arylethenesulfonyl Fluorides: Selectively Addressable Bis‐electrophiles for SuFEx Click Chemistry. Issue 45 (10th October 2016)

• Record Type: Journal Article
• Authors: Qin, Hua‐Li; Zheng, Qinheng; Bare, Grant A. L.; Wu, Peng; Sharpless, K. Barry
• Is Part Of: Angewandte Chemie international edition. Volume 55:Issue 45(2016)
• Page Start: 14155
• Page End: 14158
• Publication Date: 2016-10-10
• Subjects: β-arylethenesulfonyl fluorides -- ethenesulfonyl fluoride -- Heck–Matsuda reaction -- Michael addition -- sulfur(VI) fluoride exchange (SuFEx); Chemistry -- Periodicals; 540
• DOI: 10.1002/anie.201608807
• Languages: English
• ISSNs: 1433-7851

Abstract

Abstract: A Heck–Matsuda process for the synthesis of the otherwise difficult to access compounds, β‐arylethenesulfonyl fluorides, is described. Ethenesulfonyl fluoride (i.e., vinylsulfonyl fluoride, or ESF) undergoes β‐arylation with stable and readily prepared arenediazonium tetrafluoroborates in the presence of the catalyst palladium(II) acetate to afford the E ‐isomer sulfonyl analogues of cinnamoyl fluoride in 43–97 % yield. The β‐arylethenesulfonyl fluorides are found to be selectively addressable bis‐electrophiles for sulfur(VI) fluoride exchange (SuFEx) click chemistry, in which either the alkenyl moiety or the sulfonyl fluoride group can be the exclusive site of nucleophilic attack under defined conditions, making these rather simple cores attractive for covalent drug discovery. Abstract : Make it SuFEx‐able ! A Heck–Matsuda process for the synthesis of the otherwise difficult to access β‐arylethenesulfonyl fluorides is described. The compounds are found to be selectively addressable bis‐electrophiles for sulfur(VI) fluoride exchange (SuFEx) click chemistry, in which either the vinyl moiety or the sulfonyl fluoride group can be the exclusive site of nucleophilic attack.