Journal Article

Arylation of hydrocarbons enabled by organosilicon reagents and weakly coordinating anions

Nelson, Hosea M., Bagdasarian, Alex L., Popov, Stasik, Shao, Brian

2017

Overview

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).

• Publisher: American Association for the Advancement of Science,The American Association for the Advancement of Science
• Subject: Alkanes / Alkylation / Anions / Aromatic compounds / Benzene / Carborane / Cations / Chemical bonds / Chemists / Equivalence / Fluorides / Fluorine / Hydrocarbons / Hydrogen bonding / Hydrogen bonds / Intermediates / Methane / Reagents / Silicon