The behavior of 1,2-bis[(R)-2-(1-methoxymethoxyethyl)-3-benzo[b]thienyl] hexafluorocyclopentene before and upon UV irradiation and during thermal evolution of the photoirradiated solution has been thoroughly investigated by multinuclear NMR spectroscopy. A dynamic NMR study of the initial state was performed, providing a detailed description of the perceived conformational processes in the system. Before irradiation, three open conformations are in equilibrium, whereas UV irradiation generated the two expected cyclized diastereomers. The minor diastereomer was thermally less stable than the major one, thus leading to an unexpected increase in the diastereoselectivity when raising the photoirradiation temperature. In addition, a long thermal evolution induced slow rearrangement of the stable diastereomer into byproducts that were identified.
