Spontaneous Generation of Aryl Carbocations from Phenols in Aqueous Microdroplets: Aromatic SN1 Reactions at the Air-Water Interface.

Abstract

Although phenol is stable in bulk water, we report an exceptional phenomenon in which phenol is spontaneously transformed into a phenyl carbocation (Ph+) in water microdroplets. The high electric field at the air-water interface is proposed to break the phenolic Csp2-OH bond, forming Ph+, which remains in equilibrium with phenol as deciphered by mass spectrometry. We detected up to 70% conversion of phenol to Ph+ in aqueous microdroplets, although catalyst-free activation of the phenolic Csp2-OH bond is challenging. This transformation is well tolerated by a wide range of electron-donating and -withdrawing substituents in phenolic compounds. The Ph+ in water microdroplets could be reacted with various nucleophiles (amine, pyridine, azide, thiol, carboxylic acid, alcohol, and 18O-water), yielding the ipso-substitution products of phenol through an aromatic SN1 mechanism. Despite the fleeting life of Ph+ in the bulk, this study demonstrates its unusual stability at the aqueous microdroplet surface, enabling its detection and transformation.