Regioselective Aromatic Borylation in an Inert Solvent<sup>†</sup>

A protocol for performing Rh catalyzed aromatic borylations in cyclohexane has been devised. Borylation at the 5-position of several 1,3-substituted aromatic species ranging from electron-rich (1,3-(NMe<sub>2</sub>)<sub>2</sub>C<sub>6</sub>H<sub>4</sub>) to electron-deficient (1,3-(CF<sub>3</sub>)<sub>2</sub>C<sub>6</sub>H<sub>4</sub>) yields the corresponding aryl boronate esters. Veratrole was selectively borylated at the 4-position, thus extending regioselectivity to 1,2-substituted benzenes. Selective borylation at the 3-position of an <i>N</i>-protected pyrrole has also been demonstrated, providing a valuable reagent for cross-coupling reactions in a single step.