Iridium-Catalyzed Sequential Silylation and Borylation of Heteroarenes Based on Regioselective C-H Bond Activation.

An iridium-catalyzed regioselective sequential silylation and borylation of heteroarenes was developed, which represents a rare example of unsymmetrical intermolecular C-H bond difunctionalization through the introduction of two different functionalities during a one-pot transformation. Although the substrate scope for the dehydrogenative silylation of heteroarenes has been limited mainly to electron-rich five-membered rings, the current reaction proceeds with both electron-rich and electron-deficient heteroarenes with the aid of heteroatom-directing C-H bond activation. The regioselectivity of the second borylation was controlled by both steric factors and the electronic effect of the silyl group installed in the first step. In combination with the classic cross-coupling reaction, this method provides rapid access to multisubstituted heteroarenes.