The Pd catalyzed α-arylation followed by Baeyer-Villiger reaction was used for the preparation of lactones bearing OMe and t-Bu groups (2-OMe and 2-t-Bu). However, all the thionation conditions investigated using Lawesson's reagent or P4S10 were unsuccessful to yield the targeted thionolactones. The lactones are rapidly converted but only complex mixtures are formed containing low amounts of the targeted thionolactone but also dithiolactone. It was already reported in the literature that there is a substituent dependance in this reaction. Moreover, Johnson and coworkers also noticed that attempts to synthesize the para-methoxy bDOT variant (Scheme 2) were unsuccessful and the preparation of the para-methyl bDOT derivatives was achieved with only 4% yield. The experimental polymerization studies were thus carried out exclusively with POT-CF3 and POT-NO2.