本論文研究包含三個部份：第一部份是利用N,N-二異丙基-10-樟腦磺醯胺25作為掌性輔助基衍生之1,3-二□環戊-4-酮化合物50和51進行不對稱醛醇反應的研究；第二部份是利用N,N-二異丙基-10-樟腦磺醯胺25作為掌性輔助基衍生之1,3-二□環戊-4-酮化合物48和50進行不對稱1,4-加成反應的研究；第三部份是利用1,3-二□環戊-4-酮化合物48進行(-)-k252a的不對稱形式合成研究。
ㄧ、在不對稱醛醇反應方面：內酯縮酮化合物50和51與醛類進行不對稱醛醇反應，得到1,2-雙醇酯化合物的前軀體61、62、63和64，產率74-91%。選擇性方面，異丁醛和1,2-二氫桂皮醛與內酯縮酮化合物50進行醛醇反應，僅得到單一的產物63b和63e；與內酯縮酮化合物51進行醛醇反應，脂肪醛為異丁醛時，僅得到單一的產物63h，為1,2-二氫桂皮醛時，選擇性也高達14:1；其他的醛醇產物選擇性由1:2到1:8。而芳香醛類與內酯縮酮化合物51進行醛醇反應，皆只得到單一的產物62f-k。
二、在不對稱1,4-加成反應方面：利用內酯縮酮化合物48和50與□,□-未飽和酸甲酯進行不對稱1,4-加成反應，皆只得到單一的產物，而且產率都相當好，77%~92%。將1,4-加成產物67b-e和68g進行水解，可合成得到(+)-trans-crobarbatic acid 72以及其相似結構之內酯衍生物73c-e和74，產率79-86%。
三、在(-)-k252a的不對稱形式合成方面：利用內酯縮酮化合物48為起始物，包含不對稱醛醇反應和烷化反應兩個關鍵步驟，共用了七步完成了(+)-furanose衍生物76的合成，總產率為47%。

The studies on the application of chiral 1,3-dioxolan-4-ones, derived from (1S)-(+)-N,N-diisopropyl-10-camphorsulfonamide 25, in asymmetric synthesis are described. This thesis consists of three parts. The first and second parts are concerned with applications of chiral 1,3-dioxolan-4-ones 48, 50 and 51 in asymmetric aldol and 1,4-addition reactions to synthesize optically active compounds. In the third part, an enantioselective formal synthesis of (+)-k252a is described.
1) Asymmetric aldol reaction: Aldol reactions of the enolates of 1,3-dioxolan-4-one 50 and 51 with various aldehydes afforded corresponding products 61, 62, 63 and 64 in 74-91% yield. The reactions of 1,3-dioxolan-4-one 50 with isobutyaldehyde or 1,2-dihydrocinnamaldehyde and of 1,3-dioxolan-4-one 51 with isobutyaldehyde afforded single product 63b, 63e and 63h. The diastereoselective ratio of the reaction of 1,3-dioxolan-4-one 51 with 1,2-dihydrocinnamaldehyde is 14 : 1. The diastereoselective ratios of the other cases are in 1 : 2 to 1 : 8. On the other hand, all of the reactions of 1,3-dioxolan-4-one 51 with various aromatic aldehydes afforded single products 62f-k as a single stereoisomer.
2) Asymmetric 1,4-addition reaction: The addition of 1,3-dioxolan-4-ones 48 and 50 to □,□-unsaturated esters afforded single product in 77%~92% yield. Subsequent hydrolysis of these adducts 67b-e and 68g give (+)-trans-crobarbatic acid 72 and 3,4-disubstituted □-lactones 73c-e and 74 with high enantiomeric excesses.
3) Enantioselective formal synthesis of (+)-k252a: A seven-step synthesis, including diastereoselective aldol and alkylation reactions, of (+)-furanose 76 from 1,3-dioxolan-4-one 48 has been achieved in 47% overall yield.

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