臺灣博碩士論文加值系統

本論文的目的在探討樟腦衍生之掌性配位基β-胺基醇及β-胺基硫醇應用於催化不對稱親核性加成反應。論文共分為三個部份，第一部份在探討(+)-MINBOL 28 (12.5 mol%)和金屬鎳(II) (0.5 mol%)形成的掌性鎳(II)錯合物催化烷基鋅試劑對α,β-不飽和共軛烯酮的不對稱1,4-加成反應，反應中不需加入任何的共配基，即可得到高達93% ee的1,4-加成產物及好的產率(84%)。

第二部份旨在探討開發新型的樟腦衍生之4-羥-脯胺醯胺58作為有機催化劑催化異丁醛和硝基烯類的不對稱1,4-加成反應，在20 mol%的有機催化劑58和5當量的水，沒有額外的添加劑，在室溫反應，可得到極佳的產率及高達92% ee的1,4-加成產物。此外，α-單取代的醛類化合物與硝基苯乙烯的共軛加成反應，在5當量的氯仿存在下可得到高達98：2的非鏡像異構物選擇性和79% ee?{88% ee的鏡像選擇性。

第三部份在探討樟腦衍生之β-胺基硫醇66 [(-)-SMOTIB]為掌性配位基催化炔基鋅試劑加成至芳香醛的不對稱加成反應之研究，建立具有光學活性的丙炔基醇；此反應在10 mol%的催化量下可達到相當好的鏡像選擇性(高達92% ee)和產率(高達97%)。

This thesis, divided into three parts, is concerned with the application of camphor-derived chiral β-amino alcohol or β-amino thiol in catalytic asymmetric conjugate addition of carbon nucleophiles to α,β-unsaturated systems and asymmetric addition reactions of organozinc to carbonyl compounds. The first part has discuss the complex of (+)-MINBOL 28 and Ni(acac)2 (12.5 mol% and 0.5 mol% respectively) catalyzes enantioselective conjugate 1,4-addition of dialkylzinc to α,β-unsaturated enones in propionitrile, giving the corresponding chiral Michael adducts in high enantioselectivities (up to 93% ee) and good yields without extra addition of any coligand.

The second part is to develop new camphor-derived (2S,4R)-4-
hydroxy-L-prolinamide 58 as organocatalyst, which is capable of catalyzing Michael addition reaction of isobutyraldehyde and nitrostyrenes. By using 20 mol% catalytic loading of organocatalyst 58 and 5.0 eq. of water without additional additive at room temperature gave chiral Michael adduct with up to 92% ee and excellent yield. Furthermore, the conjugate addition of α-substituted aldehyde to trans-β-nitrostyrene in the presence of 5.0 eq. of CHCl3 proceeded with high diastereoselectivit-
ies (up to syn/anti of 98:2) and enantioselectivities (79?{88 % ee).

The third part applied (-)-(1S,2R)-10-(N,N-diisopropylsulfonamido)-2-
morpholin-4-ylmethyl-thiaisoborneol [(-)-SMOTIB 66] as chiral ligand (10 mol% loading) in the catalytic asymmetric addition of alkynylzinc to aromatic aldehyde to build chiral propargylic alcohols skeleton in good enantioselectivities (up to 92% ee) and yields (up to 97%).

中文摘要 i
英文摘要(Abstract) iii
謝誌 v
縮寫對照表 vi
目錄 viii
圖表目錄 x
第一章 緒論 1
1.1 前 言 1
第二章 (+)-MINBOL與鎳(II)錯合物催化烷基鋅的不對稱1,4-加成
反應 11
2.1 文獻回顧 11
2.2 研究動機 22
2.3 結果與討論 25
2.4 結論 38
第三章 樟腦衍生之4-羥-脯胺醯胺催化醛類和硝基烯類
化合物的不對稱1,4-加成反應 40
3.1 文獻回顧 40
3.2 研究動機 55
3.3 結果與討論 61
3.4 結論 78
第四章 (-)-SMOTIB催化炔基鋅加成至芳香醛之不對稱加成
反應 80
4.1 文獻回顧 80
4.2 研究動機 92
4.3 結果與討論 96
4.4 結論 109
第五章 實驗部份 110
5.1 一般實驗方法 110
5.2 (+)-MINBOL與鎳(II)錯合物催化烷基鋅的不對稱1,4-
加成反應結果 112
5.3 有機催化劑51、55e、56e、58的合成和有機催化
劑58催化不對稱1,4-加成反應結果 128
5.4 (-)-SMOTIB催化炔基鋅加成至芳香醛的不對稱反應
結果 151
參考文獻 163
附錄一、核磁共振光譜圖 170
附錄二、高壓液相層析圖譜 226

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