Silyl-directed, iridium-catalyzed ortho-borylation of arenes. A one-pot ortho-borylation of phenols, arylamines, and alkylarenes

Abstract

The regioselectivity of the borylation of arenes catalyzed by the combination of 4,4'-di-tert-butylbipyridine (dtbpy) and [Ir(cod)Cl]2 has typically been governed by steric effects. We describe a strategy that makes use of a new substituent for ortho-functionalization to overcome this bias. We show that arenes containing hydrosilyl substituents on an atom attached to the arene ring undergo borylation at the position ortho to the hydrosilyl group. Using iridium-catalyzed formation of silyl ethers and silylamines from silanes and either phenols or arylamines, we have developed the ortho-borylation into a one-pot conversion of free phenols and monoprotected anilines into hydroxy- and amino-substituted organoboron derivatives.