本論文研究係探討三氟甲磺酸-3,3,5-三甲基-4-側氧基-1,5-環己二烯酯與各種烯類的 Diels-Alder 反應及其應用性。
三氟甲磺酸-3,3,5-三甲基-4-側氧基-1,5-環己二烯酯52分別與10種不同的親雙烯試劑進行分子間的 Diels-Alder 反應，可得單一產物、具高立體選擇性及位向選擇性的雙環[2.2.2]辛烯酮化合物。由理論計算發現，此類Diels-Alder反應，可由雙烯劑的最高填滿分子軌域 (HOMO) 係數與親雙烯試劑的最低未填滿分子軌域 (LUMO) 係數之相互關係加以解釋。此外，利用 RHF/STO-3G 在過渡態的探討上，也有一些成功的例子來加以證實實驗的數據。

而將所得的 Diels-Alder 產物，以鈀催化還原 (Cacchi's conditions)，可得不錯的產率，成功的印證了三氟甲磺酸-3,3,5-三甲基-4-側氧基-1,5-環己二烯酯52可做為2,6,6-三甲基-2,4-環己二烯酮28的對等物。後者易雙聚化，而三氟甲磺酸酯52為一穩定之化合物，不易進行雙聚化，較具有合成的價值。

The Diels-Alder reactions of 3,3,5-trimethyl-4-oxo-1,5-cyclo -hexadienyl trifluoromethanesulfonate 52 with several dienophiles were performed and in most of the cases cycloaddition proceeded in highly regio- and stereoselective manner to produce a single bicyclo[2.2.2]octenone derivative in good to excellent yields. Theoretical calculations based on the frontier orbital theory suggests that the HOMO of diene and the LUMO of dienophile are involved in these reactions. We have also computed the transition-state energies of the Diels-Alder reaction by ab initio RHF/STO-3G method, which supports our experimental results.
The Diels-Alder adducts obtained from the above reactions were reduced using palladium catalysis (Cacchi's conditions) to furnish the products that are identical to the adducts derived from 2,6,6-trimethyl- 2,4-cyclohexadienone (28). Thus cyclohexadienyl trifluoromethane- sulfonate 52 is a stable and non-dimerizing alternative to 2,6,6-trimethyl- 2,4-cyclohexadienone (28). Our investigations clearly showed that cyclohexa-dienone 52 is a powerful diene that react with electron-deficient dienophile to produce the corresponding Diels-Alder cycloadducts, which may have great synthetic potential.

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