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Published March 31, 2017 | Supplemental Material
Journal Article Open

Arylation of hydrocarbons enabled by organosilicon reagents and weakly coordinating anions


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 sp³ and sp² C–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).

Additional Information

© 2017, American Association for the Advancement of Science. Received for publication January 30, 2017. Accepted for publication March 9, 2017. The authors declare no competing financial interests. Support was generously provided by the University of California, Los Angeles (UCLA). We thank V. Lavallo and J. R. Gordon for assistance with the syntheses of carba-closo-monocarborane anions, K. N. Houk and E. M. Sletten for useful discussions regarding mechanism, N. K. Garg and A. M. Spokoyny for assistance in manuscript preparation, the UCLA Molecular Instrumentation Center for NMR instrumentation, and the Mass Spectrometry Facility at the University of California, Irvine. Experimental procedures and characterization data are provided in the supplementary materials.

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