title: Arylation of hydrocarbons enabled by organosilicon reagents and weakly coordinating anions.
abstract: Over the past 80 years, phenyl cation intermediates have been implicated in a variety of C-H arylation reactions. Although these examples have inspired several theoretical and mechanistic studies, aryl cation equivalents have received limited attention in organic methodology. Their high-energy, promiscuous reactivity profiles have hampered applications in selective intermolecular processes. We report a reaction design that overcomes these challenges. Specifically, we found that β-silicon-stabilized aryl cation equivalents, generated via silylium-mediated fluoride activation, undergo insertion into sp3and sp2C-H bonds. This reaction manifold provides a framework for the catalytic arylation of hydrocarbons, including simple alkanes such as methane. This process uses low loadings of Earth-abundant initiators (1 to 5 mole percent) and occurs under mild conditions (30° to 100°C).
authors.affiliation: Department of Chemistry and Biochemistry, University of California, Los Angeles, CA 90095, USA.
authors.forename: Brian
authors.identifier: 0000-0002-4259-9803
authors.initials: B
authors.lastname: Shao
authors.affiliation: Department of Chemistry and Biochemistry, University of California, Los Angeles, CA 90095, USA.
authors.forename: Alex L
authors.identifier: 0000-0003-2281-8068
authors.initials: AL
authors.lastname: Bagdasarian
authors.affiliation: Department of Chemistry and Biochemistry, University of California, Los Angeles, CA 90095, USA.
authors.forename: Stasik
authors.identifier: 0000-0002-8870-0807
authors.initials: S
authors.lastname: Popov
authors.affiliation: Department of Chemistry and Biochemistry, University of California, Los Angeles, CA 90095, USA. hosea@chem.ucla.edu.
authors.forename: Hosea M
authors.identifier: 0000-0002-4666-2793
authors.initials: HM
authors.lastname: Nelson