Predominant O-alkylation in the gas-phase attack of t-butyl cations on phenol and anisole

Abstract

In the gas-phase attack of t-C₄H₉⁺ ions, obtained in the dilute gas state from the radiolysis of neopentane, on phenol and anisole, the competition between n-type and π-type nucleophilic centres of the ambident substrates is strongly biased in favour of the oxygen atom, leading to the predominant formation of the t-butylated oxonium ions as the major reaction intermediates.