Novel Synthesis of Desymmetrized Resorcinol Derivatives:  Aryl Fluoride Displacement on Deactivated Substrates

A short, high-yielding synthesis of differentially substituted resorcinol derivatives has been developed that utilizes 1,3-difluorobenzene as the starting material and employs sequential nucleophilic aromatic substitution (S_NAr) reactions to generate desymmetrized products. The scope and limitations of the second S_NAr reaction on the deactivated 1-alkoxy-3-fluorobenzene intermediates have been investigated. This methodology has also been employed in the synthesis of desymmetrized catechol derivatives from 1,2-difluorobenzene.