Intermolecular sp³C‐H Metalation of Non‐Nucleophilic Brønsted Bases Using Simple Lewis Acids

2,6‐Di‐tert‐butyl substituted pyridines (tBu2‐py) are widely used non‐nucleophilic Brønsted bases. Their ubiquity is due to their highly hindered basic site and chemically robust nature. Herein we report that simple M2X6 Lewis acids (M = Al or Ga, X = Cl, Br or I) effect intermolecular sp3C‐H metalation of tBu2‐py bases under mild conditions. The sp3C‐H metalated products can be converted in‐situ into ‐BPin, ‐iodo, ‐bromo and ‐hydroxy derivatives for further elaboration. Mechanistic investigations indicate that: (i) a frustrated Lewis pair effects sp3C‐H heterolysis to form the C‐M bond and a protonated pyridine; (ii) C‐H metalation requires singly halide‐bridged super‐electrophilic M2X6 dimers for sufficiently low barriers. Finally, sp3C‐H metalation using M2X6 is not limited to tBu2‐py bases. Thus, it is important to be aware of this facile sp3C‐H functionalisation when using a range of non‐nucleophilic Brønsted bases.