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The reaction mechanism, ligand and norbornene effects, and origins of meta-selectivity in Pd/norbornene-catalyzed alkylation and arylation via C–H activation are theoretically elucidated by DFT computation. The reaction proceeds through six major steps: ortho-C–H activation, norbornene insertion into Pd–C bonds, meta-C–H activation, meta-C–C bond formation, β-carbon elimination, and protodemetallation. Both ortho-C–H and meta-C–H activations undergo a concerted metalation–deprotonation pathway. The meta-C–C bond formation, which is the selectivity-determining step, follows a Pd(IV) pathway via oxidative addition on a Pd(II) five-membered-ring intermediate. The oxidative addition of alkyl iodide adopts an SN2 pathway, whereas aryl iodide prefers concerted oxidative addition rather than the SN2 pathway. The Pd(II) pathway via meta-C–C reductive coupling on dinuclear palladium species is not the dominant pathway because of the low concentration of Pd(0)L2. For methylation, with norbornene and pyridine (or its derivative) as ligands, the C–C reductive coupling and C–C reductive elimination from the Pd(IV) intermediate are found to be the selectivity-determining steps for meta-functionalization and benzocyclobutene formation, respectively, whereas the use of large ligands such as acridine and quinoline-type ligands (L1 and L2) moves the selectivity-determining step back to the oxidative addition and the C–C reductive elimination steps on the Pd(II) intermediate. The geometric and electronic properties of L1 and L2 further suppress the benzocyclobutene formation by increasing the energy difference between meta-functionalization and benzocyclobutene formation. The combination of 2-carbomethoxynorbornene and L2 promotes meta-ethylation and -arylation by disfavoring the C–C reductive elimination steps from the Pd(II) and Pd(IV) intermediates as well as slightly favoring the oxidative addition step.

Reaction mechanism, norbornene and ligand effects, and origins of meta-selectivity of Pd/norbornene-catalyzed C–H activation