儘管茚滿酮之不對稱合成已有相當程度之發展，在銠金屬催化下使用親核試劑對α,β-不飽和烯酯進行加成後，經由1,4-轉移再對酯基進行加成之茚滿酮合成案例在過去僅有一例被報導過。因此，我們在此篇論文中設計了一種新穎結構之化合物1，結合α,β-不飽和烯酯與Hiyama教授發表過之矽試劑結構，成功地在掌性銠錯合物之催化下，使用催化量之四苯硼鈉作為反應之起始親核試劑，得到大於50%的產率和最高99%之ee值。
除此之外，我們也藉由修飾此受質不飽和β位上和矽官能基上之芳香取代基，來檢視銠金屬不對稱1,4-轉移之可能。我們最終發現在特定雙烯配位基配位之掌性銠錯合物催化下，1,4-銠金屬轉移偏好發生在加成之芳香基，並生成絕對組態(R)-構型之茚滿酮產物。

The asymmetric synthesis of indanone has already been well-developed, but there is still only one case of rhodium-catalyzed enoate addition following with 1,4-rhodium shift with addition to ester to give the chiral indanones. In this thesis, we developed a design of a new-type starting compound 1 combining β-monosubstituted α,β-unsaturated ester with organosilicon substituent to give a new possibility for the rhodium-catalyzed asymmetric synthesis of indanones. In this reaction, we successfully used a catalytic amount of the sodium tetraarylborate as the nucleophile to initiate the catalytic cycle and reached the target indanone products up to 53% yield and 99% ee.
In addition, we also try to inspect the asymmetric 1,4-rhodium shift by modifying the starting compounds with different pairs of aryl group. We finally found that for some of the diene rhodium complex, the 1,4-rhodium shift is more preferred to the addition aryl group after the enoate addition step and then to give the (R)-form indanone product favorably.

摘要 i
Abstract ii
謝誌 iii
目錄 iv
式目錄 vi
表目錄 viii
圖目錄 ix
Abbreviation Table xi
第一章、 緒論 1
第二章、 文獻回顧 4
第一節、 銠金屬催化之不對稱1,4-加成反應 4
第二節、 芳香基苯甲醇二甲基矽烷之偶合反應與其於銠金屬催化之不對稱1,4-加成反應之應用 11
第三節、 銠金屬之1,4-轉移現象以及銠金屬催化之茚滿酮不對稱合成案例之分析 13
第三章、 結果與討論 25
第一節、 初步反應測試與最佳化之反應條件 25
第二節、 3,5-二甲苯取代基之受質檢視與探討 33
第三節、 苯甲醚取代基之受質檢視與探討 40
第四節、 苯基取代基之受質檢視與探討 51
第五節、 結論 61
第四章、 Instrument, chemicals, experiment procedures, and Analysis of sprctrum 62
第一節、 Instrument 62
第二節、 Chemicals 64
第三節、 Experimental procedures and Analysis of spectrum 65
參考文獻 108
附錄、NMR光譜 S1

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