本篇論文探討利用一價銠金屬試劑與掌性雙環雙烯配基所形成的錯合物催化不對稱加成反應生成具有掌性中心的胺類化合物。內容分成下面兩個部分。
一、 利用一價銠金屬催化有機硼酸對脂肪族醛亞胺進行不對稱芳基化反應 : 合成憶思能及NPS-R-568衍生物
利用一價銠金屬催化劑與掌性雙環[2.2.1]雙烯配基L1g所形成的錯合物催化芳香基硼酸試劑11對脂肪族醛亞胺14進行不對稱加成反應。所得到一系列掌性芳香基脂肪胺化合物，產率有25–99%，鏡像超越值94–＞99.5%。再將具有掌性中心的芳香基脂肪胺化合物經由數步反應步驟去合成目標藥物億思能及NPS-R-568衍生物。
二、 利用一價銠金屬與掌性雙烯配基所形成的錯合物催化共軛重氮酯類化合物與芳香胺進行加成反應
利用一價銠金屬與掌性雙環[2.2.2]雙烯配基L3c所形成的錯合物催化β,γ-不飽和重氮酯類化合物83形成銠-碳烯中間產物，使芳香胺類化合物84對其進行具有位置選擇性的不對稱加成反應。所得到一系列具有掌性中心的γ胺基α,β-不飽和酯類化合物90有23–90%的產率與47–99%的鏡像超越值。
關鍵詞：一價銠金屬、掌性雙環雙烯配基、不對稱加成反應、憶思能、共軛重氮酯類化合物。

This thesis describes the syntheses of chiral amines from the asymmetric addition reactions catalyzed by the complexes generated from Rh(I) and bicyclo[2.2.1]chiral diene ligands. The content is divided into the following two parts.
I. Rh-Catalyzed Asymmetric Arylation of Aliphatic Aldimines: Syntheses of Rivastigmine and NPS-R-568 Thio Analogue.
A Rh(I)-catalyzed enantioselective arylation of aliphatic aldimines is reported in this work. In the presence of 3.0 mol % of Rh(I)-catalyst in situ generated from the [RhCl(C2H4)2]2 pre-catalyst and chiral bicyclo[2.2.1]heptadiene ligand L1g, addition reactions of aryl boronic acids 11 with aliphatic aldimines 14 afforded the desired products in 25–99% yields and with 94–＞99.5% ee’s. Syntheses of Rivastigmine and NPS-R-568 thio analogue were achieved to demonstrate the synthetic potential of this method.
II. Regioselective and Enantioselective Addition of Arylamines to Conjugate Diazoester Catalyzed by Rh(I)/Chiral Diene Complexes
This work describes the regioselective and enantioselective addition of arylamines 84 to conjugate diazoester 83 catalyzed by a catalyst in situ generated from [RhCl(C2H4)2]2 pre-catalyst and chiral bicyclo[2.2.2]octadiene ligand L3c. The asymmetric addition reaction afforded predominantly amines 90 in 25–99% yields and with 96–＞99.5% ee’s.
Key words: Rhodium (I)、Bicyclo[2.2.1]chiral diene ligands、Asymmetric addition、Rivastigmine、Conjugate Diazoester.

參考文獻
1. Smith, S.W. Toxicol Sci. 2009, 110, 4–30.
2. Nemeth, E. F. Jouranl of Molecular Endocrinology. 2002, 29, 15–21.
3. Pablo Urena Torres, M.D. Journal of Renal Nutrition. 2006, 16, 253–258.
4. Bayer, T. BMJ. 1999, 318, 633–638.
5. Kuriyama, M.; Soeta, T.; Hao, X.; Chen, Q.; Tomioka, K. J. Am. Chem. Soc. 2004, 126, 8128–8129.
6. Jagt, R. B. C.; Toullec, P. Y.; Geerdink, D.; de Vries, J. G.; Feringa, B. L.; Minnaard, A. J. Angew. Chem. Int. Ed. 2006, 45, 2789–2791.
7. Duan, H. -F.; Jia, Y.-X.; Wang, L.-X.; Zhou, Q.-L. Org. Lett. 2006, 8, 2567–2569.
8. Tokunaga, N.; Otomaru, Y.; Okamoto, K.; Ueyama, K.; Shintani, R.; Hayashi, T. J. Am. Chem. Soc. 2004, 126, 13584–13585.
9. Otomaru, Y.; Tokunaga, N.; Shintani, R.; Hayashi, T. Org. Lett. 2005, 7, 307–310.
10. Wang, Z.-Q.; Feng, C.-G.; Xu, M.-H.; Lin, G.-Q. J. Am. Chem. Soc. 2007, 129, 5336–5337.
11. Cao, Z.; Du, H. Org. Lett. 2010, 12, 2602–2605.
12. Zhao, G.-Z.; Sipos, G.; Salvador, A.; Ou, A.; Gao, P.; Skelton, B. W.; Dorta, R. Adv. Synth. Catal. 2016, 358, 1759–1766.
13. Jiang, T.; Chen, W.-W.; Xu, M.-H. Org. Lett. 2017, 19, 2138–2141.
14. Trincado, M.; Ellman, J. A. Angew. Chem. Int. Ed. 2008, 47, 5623–5626.
15. Cui, Z.; Yu, H.-J.; Yang, R.-F.; Gao, W.-Y.; Feng, C.-G.; Lin, G.-Q. J. Am. Chem. Soc. 2011, 133, 12394–12397.
16. Kato, N.; Shirai, T.; Yamamoto, Y. Chem. Eur. J. 2016, 22, 7739–7742.
17. Qian, X.-W.; Xue, Z.-J.; Zhao, Q.; Cui, Z.; Chen, Y.-J.; Feng, C.-G.; Lin, G.-Q. Org. Lett. 2017, 19, 5601–5604.
18. Chen, C.-C.; Gopula, B.; Syu, J.-F.; Pan, J.-H.; Kuo, T.-S.; Wu, P.-Y.; Henschke, J. P.; Wu, H.-L. J. Org. Chem. 2014, 79, 8077–8085.
19. Gopula, B.; Chiang, C.-W.; Lee, W.-Z.; Kuo, T.-S.; Wu, P.-Y.; Henschke, J. P.; Wu, H.-L. Org. Lett. 2014, 16, 632–635.
20. 黃普航 (2016)。碩士論文，國立台灣師範大學化學研究所，台北，台灣。
21. Chiang, P.-F.; Li, W.-S.; Jian, J.-H.; Kuo, T.-S.; Wu, P.-Y.; Wu, H.-L. Org. Lett. 2018, 20, 158–161.
22. Syu, J.-F.; Lin, H.-Y.; Cheng, Y.-Y.; Tsai, Y.-C.; Ting, Y.-C.; Kuo, T.-S.; Janmanchi, D.; Wu, P.-Y.; Henschke, J. P.; Wu, H.-L. Chem. Eur. J. 2017, 23, 14515–14522.
23. 吳文茜 (2012)。碩士論文，國立台灣師範大學化學研究所，台北，台灣。
24. 潘治翰 (2012)。碩士論文，國立台灣師範大學化學研究所，台北，台灣。
25. Uozumi, Y.; Lee, S.-Y.; Hayashi, T. Tetrahedron Lett. 1992, 33, 7185–7188
26. Wei, W.-T.; Yeh, J.-Y.; Kuo, T.-S.; Wu, H.-L. Chem. Eur. J. 2011, 17, 11405–11409.
27. Abele, S.; Inauen, R.; Spielvogel, D.; Moessner, C. J. Org. Chem. 2012, 77, 4765–4773.
28. Singelton, D. A.; Thomas, A. A. J. Am. Chem. Soc. 1995, 117, 9357–9358.
29. Abdel-Magid, A. F.; Carson, K. G.; Harris, B. D.; Maryanoff, C. A.; Shah, R. D. J. Org. Chem. 1996, 61, 3849–3862.
30. Yamazaki, N.; Atobe, M.; Kibayashi, C. Tetrahedron Lett. 2001, 42, 5029–5032.
31. Mangas-Sanchez, J.; Rodrıguez-Mata, M.; Busto, E.; Gotor-Fernandez, V.; Gotor, V. J. Org. Chem. 2009, 74, 5304–5310.
32. Demonceau, A.; Simal, F.; Noels, A. F. Tetrahedron Lett. 1997, 38, 7879–7882.
33. Nishimura, T.; Maeda, Y.; Hayashi, T. Angew. Chem. Int. Ed. 2010, 49, 7324–7327.
34. Chen, D.; Zhang, X.; Qi, W.-Y.; Xu, B.; Xu, M.-H. J. Am. Chem. Soc. 2015, 137, 5268–5271.
35. Chen, D.; Zhu, D.-X.; Xu, M.-H. J. Am. Chem. Soc. 2016, 138, 1498–1501.
36. Liu, Y.; Zhou, C.; Xiong, M.; Jiang, J.; Wang, J. Org. Lett. 2018, 20, 5889–5893.
37. Ma, X.; Jiang, J.; Lv, S.; Yao, W.; Yang, Y.; Liu, S.; Xia, F.; Hu, W. Angew. Chem. Int. Ed. 2014, 53, 13136–13139.
38. Moore, S. A.; Shuker, D. E. G. J. Label Compd. Radiopharm. 2011, 54, 855–858.
39. Doyle, M. P.; Yan, M.; Hu, W.; Gronenberg, L. S. J. Am. Chem. Soc. 2003, 125, 4692–4693.
40. Padwa, A.; Kulkarni, Y. S.; Zhang, Z. J. Org. Chem. 1990, 55, 4144–4153.