Highly Regioselective Remote Lithiation of Functionalized 1,3‐bis‐Silylated Arenes

Substituted arenes flanked by two bulky triethylsilyl groups were regiospecifically lithiated at the 5‐position with nBuLi?PMDTA at 25 °C. The resulting aryllithiums reacted with a broad range of electrophiles such as ketones, isocyanates, Weinreb amides, allyl bromides, and CO₂ at 25 °C. These bis‐silylated arenes were then converted in simple reaction sequences into silyl‐free tetrasubstituted arenes. This remote lithiation was extended to 2,6‐bis(triethylsilyl)pyridine as well as 3,3′‐bis(triethylsilyl)biphenyl.