title: A Heck-Matsuda Process for the Synthesis of β-Arylethenesulfonyl Fluorides: Selectively Addressable Bis-electrophiles for SuFEx Click Chemistry.
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.
authors.affiliation: Department of Chemistry, The Scripps Research Institute, La Jolla, CA, 92037, USA.|School of Chemistry, Chemical Engineering and Life Science, Wuhan University of Technology, Wuhan, Hubei Province, 430070, China.
authors.forename: Hua-Li
authors.initials: HL
authors.lastname: Qin
authors.affiliation: Department of Chemistry, The Scripps Research Institute, La Jolla, CA, 92037, USA.
authors.forename: Qinheng
authors.identifier: 0000-0002-8440-8673
authors.initials: Q
authors.lastname: Zheng
authors.affiliation: Department of Chemistry, The Scripps Research Institute, La Jolla, CA, 92037, USA.
authors.forename: Grant A L
authors.initials: GA
authors.lastname: Bare
authors.affiliation: Department of Chemical Physiology, The Scripps Research Institute, La Jolla, CA, 92037, USA. pengwu@scripps.edu.
authors.forename: Peng
authors.initials: P
authors.lastname: Wu
authors.affiliation: Department of Chemistry, The Scripps Research Institute, La Jolla, CA, 92037, USA. sharples@scripps.edu.
authors.forename: K Barry
authors.initials: KB
authors.lastname: Sharpless
mesh_terms: D057930:Click Chemistry; D005030:Ethylenes / Q000138:chemical synthesis* / Q000737:chemistry; D015394:Molecular Structure; D013441:Sulfinic Acids / Q000138:chemical synthesis* / Q000737:chemistry
chemical_list: D005030:Ethylenes; D013441:Sulfinic Acids; C048899:sulfuryl fluoride; C036216:ethylene
keywords: Heck-Matsuda reaction; Michael addition; ethenesulfonyl fluoride; sulfur(VI) fluoride exchange (SuFEx); β-arylethenesulfonyl fluorides