Exploiting Alkylquinone Tautomerization: Amine Benzylation

A general protocol for the synthesis of benzylic amines via side-chain amination of alkylquinones is reported. The reactions are initiated by the tautomerization of an alkylquinone to the corresponding quinone methide, which is subsequently trapped in situ by an amine nucleophile. This process is promoted by tertiary amines in protic solvents under mild conditions and is compatible with many functional groups. 1,2- and 1,4-benzoquinones, as well as naphthoquinones, participate in this reaction using a wide range of primary and secondary amines/anilines. The synthetic utility of this transformation is also explored.