Modulating the reaction pathway of phenyl diazonium ions using host–guest complexation with cucurbit[7]uril

Abstract

Aryl diazonium ions are known to be an important intermediate in the divergent synthesis of azo compounds and substituted aromatics. The presence of more than one electrophilic center in a diazonium ion could lead to undesirable side reactions during a synthesis. Herein, we report that the electrophilic α-carbon on a phenyl diazonium [PhN2]+ ion can be selectively deactivated upon host–guest complexation with cucurbit[7]uril (CB7) in aqueous media, achieving a ∼60-fold increase in the half-life of [PhN2]+. Notably, however, the electrophilic nitrogen of the encapsulated diazonium ion remains active towards diazo coupling with strong nucleophiles, allowing the formation of azo compounds using a two-month-old aqueous solution of [CB7–PhN2]+. Our supramolecular approach can open new possibilities for the reactive chemistry of organic molecules in aqueous media.