本論文的內容分成三個部份，第一部份為樟腦磺醯胺衍生物之掌性1,3-二㗁環戊-4-酮化合物於不對稱tofacitinib的合成研究，第二部份利用相同的樟腦磺醯胺衍生物之掌性1,3-二㗁環戊-4-酮化合物於不對稱串聯反應之研究，第三部份研究釩金屬促進樟腦醯胺衍生物之掌性亞胺甘胺酸酯進行氧化耦合反應。
第一部份：我們以1,3-二㗁環戊-4-酮化合物36與巴豆酸甲酯的Michael加成產物52g為起始物完成藥物tofacitinib前驅物的不對稱合成，總合成步驟只需8步即可快速且有效率的得到具有光學活性之tofacitinib的前驅物75，總產率為26%，其中有效的使用苯甲胺在沒有溶劑的條件下將輔助基移除，並在最後經過中間不須純化的連續三個反應步驟合成前驅物75，而化合物75可由文獻已知方法再行3個反應步驟即可得到tofacitinib。
第二部份：由1,3-二㗁環戊-4-酮化合物36或38與α,β-不飽和酯進行Michael反應，先建立兩個連續的掌性中心後，再接著進行α-取代反應來得到第三個連續的掌性中心，其中前兩個掌性中心的建立皆可以達到大於98%非鏡像選擇性，第三個掌性中心分別可以有40/1到大於99/1與5/1到大於99/1的非鏡像選擇性；另外在一鍋化反應條件下進行Michael-allylation可以有效地得到與逐步反應相似的產率與非鏡像選擇性；除此之外，1,3-二㗁環戊-4-酮化合物38亦可與雙取代的α-甲基巴豆酸甲酯反應，搭配掌性化合物87提供質子可得到α-非鏡像選擇性反轉的產物，其非鏡像選擇性大於99/1。
第三部份：我們利用五價氧釩金屬促進樟腦醯胺衍生物84進行不對稱氧化耦合反應，其反應先經由烯醇硼中間體再藉由五價氧釩氧化後可以控制得到單一非鏡像選擇性自身氧化耦合產物，其自身氧化耦合產物97可以簡單地經由過濾收集，將化合物97水解去除輔助基後的雙胺產物98在有機合成上具有廣泛的應用性。

This thesis consists of three parts. The first part reports formal asymmetric synthesis of (+)-tofacitinib by camphor sulfonamide derived 1,3-dioxolan-4-one. The second part reports stereoselective cascade Michael-alkylation/oxidation reactions by the same 1,3-dioxolan-4-one. The third part focuses on oxovanadium(V) mediated asymmetric oxidative homo-coupling of boron enolate from camphor derived iminoglycinate.
Part I: We reported a concise formal asymmetric synthesis of (+)-tofacitinib from chiral 1,3-dioxolan-4-one 36, which was elaborated through a highly stereoselective Michael addition in 8 steps with 26% overall yield. The synthesis features a solvent-free removal of chiral auxiliary, a ring cyclization to furnish chiral imide 63 and a sequencial reactions (oxidation, reductive amination and SNAr reaction). The precursor cis-75 could be transformed to tofacitinib by a reported procedure in three steps.
Part II: Stereoselective Michael addition of 1,3-dioxolan-4-one with α,β-unsaturated ester followed by stepwise alkylation/oxidation could obtain α-hydroxy-1,3-diester subunit with three contiguous stereogenic centers in up to 91% yield and 99% de. Stereoselective cascade Michael-allylation 1,3-dioxolan-4-one 38 with methyl crotonate followed by allylation in one-pot could obtain the result similar to stepwise process. Inversion of stereochemistry at α-position could be achieved by using Michael acceptor equipped with a suitable group followed by a highly stereoselective protonation.
Part III: Conversion of iminoglycinate 84 to boron enolate followed by the treatment of oxovanadium reagent could furnish the homo-coupling product in one-pot. After optimization of the reaction condition, single enantiomer could be obtained with satisfactory yield. The homo-coupling product 97 could be collected by filtration, and the hydrolyzed diamino diester 98 is a useful subunit for further applications.

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