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.