Appending aromatic moieties at the para- and meta-position of calixarene phenol rings via p-bromodienone route

The silver-mediated nucleophilic substitution on calixarene p-bromodienone derivatives (the ‘p-bromodienone route’) with activated aromatic substrates allows the introduction of aromatic moieties at the para- or meta-position of calixarene aromatic rings. Less reactive substrates mainly afford C–O para-coupled derivatives, while more activated ones mainly give inherently chiral, C–C meta-coupled products through a dienone–phenol rearrangement of the intermediate dienone derivative. Examples of C–C para-coupling and O–C coupling at the endo calixarene oxygen atom were also observed.