After validating our theoretical model through the study of experimental results reported by Johnson et al. on substituted DOT and simulating the substitution of various EWG/EDG on POT thionolactone, the next step consisted in the preparation of a selection of these thionolactones. NO2 and CF3 were chosen as EWG, and OMe and t-Bu as EDG. 7-(4-trifluoromethylphenyl) oxepane-2-thione (POT-CF3) and 7-(4-nitrophenyl) oxepane-2-thione (POT-NO2) were prepared in three steps from cyclohexanone (scheme 2). Starting from 4bromobenzotrifluoride, 1-CF3 was obtained (64% yield) by Pd catalyzed α-arylation. The presence of the NO2 group hampered this reaction for 1-NO2, but metal-free α-arylation under aerobic conditions in the presence of NaOtBu enabled its preparation, although in lower yield (37%). Baeyer-Villiger oxidation was next performed to obtain the corresponding lactones 2-CF3 and 2-NO2, in good to excellent yields (yield of 62 and 94%, respectively). The final critical step is the thionation of the lactones. Using Lawesson's reagent in anhydrous toluene, yielded POT-CF3 with a yield of 35% (Scheme 2). The same procedure did not allow the isolation of POT-NO2, due to purifications issues. Utilization of P4S10 in HMDO/CH3CN rendered purification easier and POT-NO2 could be obtained in a 29% yield that is in line with those typically reported for this type of compounds.