Direct functionalization of aromatic substituents on [28]hexaphyrin was achieved by Ir-catalyzed borylation with the Smith-Miyaura-Hartwig protocol. High para. selectivity was observed in the reaction on 2,6-dichlorophenyl and 2,6-dimethoxyphenyl substituents of [28]hexaphyrin. The reaction with [26]hexaphyrin resulted only in reduction of the substrate to provide [28]hexaphyrin without borylation, thus highlighting the importance of the oxidation state of substrates in this catalytic transformation. The borylated hexaphyrin can be used for Suzuki-Miyaura cross-coupling reaction. (c) 2008 Elsevier Ltd. All rights reserved.