A series of novel (E)-5,5-dimethyl-3-styrylcyclohex-2-en-1-ol dienes were synthesized by reduction of the respective ketones and their Diels-Alder reactivity explored with Nphenylmaleimide and methyl acrylate. Consequently, two groups of novel products were synthesized in high yields. In reactions with N-phenylmaleimide, the initially formed cycloadducts undergo an additional in situ lactonization to give tricyclic lactone systems, due to spontaneous attack of the allylic hydroxyl on the neighboring carbonyl group of the dienophile residue. All reactions proceeded stereoselectively to give solely the endo products.