The Diels -Alder reactions between hemicyclone and a number of substituted benzoquinones are reported. Photolysis of the products produces pentacyclo [5,4,0,02,6,03,10,05,9] undecane derivatives and/or 2- oxapentacyclo [6,4,0,01,4,03,7,05,9] dodecane derivatives depending on the substituents. X-ray crystal structures of oxetan (8) and cyanohydrin (33) are also reported.