Iridium‐Catalyzed,Silyl‐Directed,peri‐Borylation of C−H Bonds in Fused Polycyclic Arenes and Heteroarenes

peri‐Disubstituted naphthalenes exhibit interesting physical properties and unique chemical reactivity, due to the parallel arrangement of the bonds to the two peri‐disposed substituents. Regioselective installation of a functional group at the position peri to 1‐substituted naphthalenes is challenging due to the steric interaction between the existing substituent and the position at which the second one would be installed. We report an iridium‐catalyzed borylation of the C−H bond peri to a silyl group in naphthalenes and analogous polyaromatic hydrocarbons. The reaction occurs under mild conditions with wide functional group tolerance. The silyl group and the boryl group in the resulting products are precursors to a range of functional groups bound to the naphthalene ring through C−C, C−O, C−N, C−Br and C−Cl bonds.