中文摘要
在有機合成領域中，經由Diels-Alder環化加成反應建立具有六員環骨架之分子，是一非常重要的合成方法。在本論文中，我們利用一個新的合成方法，更快速而有效的合成立體空間擁擠的六員環化合物。以化合物18作為起始物和酮類及醛類進行Knoevenagel縮合反應，生成化合物19及22。以化合物19為親二烯與2-甲基-1,3-戊二烯進行Diels-Alder反應得到六員環化合物28；以化合物22為親二烯和反式-1,3-戊二烯進行Diels-Alder環化加成反應則可得到兩個具有立體選擇性的化合物34及35。再運用萘化鋰試劑進行還原去氰取代反應引進不同的親電子基，得到化合物41、42及47。利用此方法，我們可成功的將α-氰基-α,β-不飽和酮作為空間擁擠之烯酮類化合物之對等物，促進Diels-Alder環化加成反應的進行，並藉由親二烯化合物上不同的官能基，得到具有立體選擇性的六員環產物。此新發展的合成方法，具有高產率、高幾何及高立體選擇性，預期在未來可有效的應用於具有複雜結構化合物之有機合成上。

English Abstract
Construction of cyclohexane adducts via Diels-Alder reaction is an important issue in synthesis of natural products. This thesis describes an organic chemistry methodology development which is a novel process for the construction of highly congested cyclohexanes. The α-cyano-α,β- unsaturated ketones 19 and 22 can readily be prepared from the substituted acetonitriles 18 and ketones or aldehydes via a Knoevenagel condensation process. As we chose α-cyano-α,β-unsaturated ketone 19 as a dienophile, the Diels-Alder reaction with isoprene gave cyclohexane adduct 28, which obeyed the ortho-para rule respectively. When α-cyano-α,β-unsaturated ketone 22 acted as a dienophile, the Diels-Alder rection with 1,3-pentadiene gave stereoselective adducts 34 and 35. These cycloadducts was then treated with lithium naphthalenide followed by the addition of alkylating reagent methyl iodide or allyl bromide to give product 41, 42 and 47. Through this process, α-cyano-α,β-unsaturated ketones can be demonstrated to be a functional dienophile and act as equivalents of congested enones in Diels-Alder reaction. This process can also get stereoselective cyclohexanes through different functional groups on dienophiles. Thus, this newly developed process can expectably be utilized in structurally complex targets in organic synthesis.

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