Mild iridium-catalyzed borylation of arenes. High turnover numbers, room temperature reactions, and isolation of a potential intermediate.

Abstract

The borylation of arenes leads to the formation of synthetically versatile products from unactivated arene reagents. We report that Ir(I) precursors in conjunction with bipyridine ligands catalyze in high yields the borylation of arenes under mild conditions. These reactions encompase arenes bearing both electron-withdrawing and electron-donating substituents. The temperatures required for the transformation are much lower than those previously reported for direct arene borylation. The combination of [Ir(COE)2Cl]2 and (4,4-di-t-butyl)bipyridine even allows for reaction at room temperature. The same catalyst system at 100 degrees C provides remarkably high turnover numbers for a hydrocarbon functionalization process. Mechanistic studies show that the reactions involve uncommon, Ir(II) tris-boryl complexes. An example of this type of complex ligated by di-t-butylbipyridine was isolated and structurally characterized. It reacted rapidly at room temperature to produce aryl boronate esters in high yields.