A new system for catalytic arylation and alkenylation of alkane segments has been developed. The ortho-tert-butylaniline substrates and 2-pivaloylpyridine may be arylated and alkenylated at the tert-butyl group, while no functionalization occurred at more reactive C-H and other bonds. Arylation and alkenylation of these substrates are achieved in the presence of Ph2Si(OH)Me and Ph-CH=CH-Si(OH)Me2, respectively, and the catalytic amount of Pd(OAc)2 and stoichiometric oxidant (Cu(OAc)2, 2 equiv) in DMF. In contrast, the ortho-i-propylaniline substrate underwent cyclopalladation, but no arylation product was obtained. Complex compound 14 was synthesized via tandem arylation-alkenylation of tert-butylaniline 11. We hypothesize that the high selectivity of this system stems from the confluence of directing effect of the Schiff base or pyridine moiety and unique reactivity properties of a phenyl-palladium acetate species (Ph-Pd-OAc.Ln).