In summary, it has been shown the substituents on the picolinamide directing group have a significant effect on yield and selectivity of C-H functionalisation reactions conducted under silverfree conditions. A variety of electron rich and electron poor were investigated on a range of amine substrates, with the latter generally leading to lower yielding reactions. Highest yields were obtained with a methylpicolinamide directing group which gave some improvements over the unsubstituted system. Most notably, the use of typically led to increased yields of C-H arylation reactions in most cases, and also to reduced quantities of diarylation products. The beneficial effect of this directing group can perhaps tentatively be explained by accelerated decomplexation from the palladium leading to more efficient catalytic turnover, and deceleration of overarylation reactions due to the increased steric hindrance. Further improvements in reaction yields could often be obtained by performing reactions in 3-methyl-3-pentanol (tHxOH) as solvent. These conditions enabled us to obtain synthetically useful yields of arylation products from a range of substrates.