Direct Observation of C–H Cyclopalladation at Tertiary Positions Enabled by an Exo-Directing Group

Here we describe the first preparation of tertiary alkyl palladium complexes via C–H activation. Enabled by an exo-type oxime directing group, cyclopalladation occurred smoothly at the bridgehead position. Treatment of the resulting complex with iodine led to C–H iodination at the methine carbon. This study provides important mechanistic information for palladium-catalyzed functionalization of methine C–H bonds.