The synthesis and manipulation of certain Diels–Alder adducts of levoglucosenone and iso-levoglucosenone

Diels–Alder cycloaddition reactions between the biomass-derived platform molecule levoglucosenone (2) and various cyclic dienes such as α-terpinene produced a range of adducts, including compound 28. Manipulation of these adducts then afforded a series of derivatives. So, for example, reductions of the associated carbonyl groups delivered the corresponding alcohols including compound 29 and on reaction of these with diethylaminosulfur trifluoride rearranged fluorination products such as tetracycle 30 were obtained. An analogous suite of compounds was obtained by manipulation of the Diels–Alder adducts derived from reacting the same dienes with iso-levoglucosenone that was itself obtained through simple manipulation of levoglucosenone. Our earlier studies suggest that various of these derivatives could be used in the production, via ring-opening metathesis polymerisation (ROMP), of new bio-based polymers.