The selective and predictable C-H functionalization of arenes is a valuable method for the synthesis and modification of organic molecules in which regioisomer formation is often controlled by electronic factors or the presence of coordinating groups. On the other hand, the iridium-catalyzed C-H borylation of arenes can achieve unique steric-controlled regioselectivity. In this account, we describe our recent studies on the iridium-catalyzed C-H borylation of arenes: the development of novel catalytic systems that exhibit steric-controlled para-selectivity for mono- and unsymmetrically 1,2-disubstituted benzenes; and their application to the functionalization of large polycyclic aromatic hydrocarbons (molecular nanocarbons).
