Abstract The first general synthesis of bis-α-acyloxy-1, 4-and-1, 5-diketones has been accomplished in a catalytic oxidative opening of bis-acylated THF and THP (tetrahydropyran) diols, which were synthesised by osmium-or ruthenium-catalysed oxidative cyclisation of 1, 5-and 1, 6-dienes. The overall sequence corresponds to the regioselective double ketoacyloxylation of the starting diene. The synthesised bis-α- ...