[摘要]:On irradiation (350 nm) in the presence of 2,3-dimethylbuta-1,3-diene (8), 4-(alk-1-ynyl)coumarins 1 afford mixtures of cyclobuta- and cycloocta-annulated products 9 and 10, respectively. In contrast, the corresponding thiocoumarins 2 react with the same diene chemoselectively to give cyclohexa-annulated products 11.