本論文敘述以2莫耳百分比的一價銠金屬 (Rh) 與掌性雙烯配位基(chiral- diene ligand) 所形成的金屬錯合物，在最佳化條件下(24 °C，乙醇為溶劑，KHF2(aq)為添加劑)，催化芳基硼酸進行不對稱1,4-加成反應至(E)-1-嗎啉基-4-芳基丁烯-1,4-二酮 (16a)。可得一系列具有掌性中心的2-芳基-4-酮基丁醯胺產物，其產率最高可至99%，鏡像超越值最高也可達99.5%。
　　在合成應用上，以加成產物 18a作為起始物合成出α位置上為掌性四級碳中心的內酯46。此反應過程經由以NaBH4進行還原反應； 2) 酸性條件下環化成內酯，得其非鏡像異構物比例為2比1的一對非鏡像異構物45a及45b ; 3) 烷化步驟中合成出具有掌性四級碳中心的內酯46及其鏡像異構物ent-46。

This thesis describes the preparation of chiral 2,4-diaryl-4-oxobutanamindes from asymmetric conjugate addition reaction of various arylboronic acids to (E)-1-morpholino-4-arylbut-2-ene-1,4-dione 16. In the presence of 2 mol% of chiral rhodium catalyst comprising of [RhCl(C2H4)2]2 and chiral diene ligand 12e, the catalytic reaction proceeds in a high diastereoselective fashion to provide the corresponding adducts 18 with a C2-stereogenic center in up to 99% yield and >99.5% ee in EtOH using KHF2(aq) as an additive.
In the synthetic application, compound 18a was transformed into enantiomeric isomers bearing a quaternary chiral center at the α–position of lactone compound 46. The sequence of the transformation involves 1) reduction of compound 18a with NaBH4; 2) the resulting diastereomeric isomers, with an approximate ratio of 2:1, were subjected to acid-catalyzed translactonization to yield 45a and 45b, respectively; 3) respective treatment of compound 45a and 45b with LDA at −78 °C and followed by MeI offered lactone 46 and its enantiomer ent-46.

1. Chaudhuri, R. K.; Bojanowski, K. International Journal of Cosmetic Science, 2014, 36, 211.
2. Dhillon, V. S.; Husain, S. A.; Ray, G. N. Teratogen. Carcin. Mut. 2003, 23, 35.
3. Whelan, J. Drug Discovery Today 2002, 7, 90.
4. Chung, Y. C.; Janmanchi, D.; Wu, H. L. Org. Lett. 2012, 14, 2766.
5. Zigterman, J. L.; Woo, J. C. S.; Walker, S. D.; Tedrow, J. S.; Borths, C. J.; Bunel, E. E.; Faul, M. M. J. Org. Chem. 2007, 72, 8870.
6. Lu, H. H.; Wang, X. F.; Yao, C. J.; Zhang, J. M.; Wu, H.; Xiao, W. J. Chem. Commun., 2009, 4251.
7. Wang, Z.; Chen, D. H.; Yang, Z. G.; Bai, S.; Liu, X. H.; Lin, L. L.; Feng, X. M. Chem. Eur. J. 2010, 16, 10130.
8. Wang, Z.; Yang, Z. G.; Chen, D. H.; Liu, X. H.; Lin, L. L.; Feng, X. M. Angew. Chem. Int. Ed. 2011, 50, 4928.
9. Zhang, W.; Tan, D.; Lee, R.; Tong, G. H.; Chen, W. C.; Qi, B. J.; Huang, K. W.; Tan, C. H.; Jiang, Z. Y. Angew. Chem. Int. Ed. 2012, 51, 10069.
10. Feng, X. Q.; Du, H. F. Asian J. Org. Chem. 2012, 1, 204.
11. Zeise, W. C. Ann. Phys. 1831, 97, 497.
12. Cope, A. C.; Howell, C. F.; Knowles, A. J. Am. Chem. Soc. 1962, 84, 3191.
13. Hosokawa, T.; Okuda, C.; Murahashi, S. J. Org. Chem. 1985, 50, 1282.
14. Hayashi, T.; Ueyama, K.; Tokunaga, N.; Yoshida, K. J. Am. Chem. Soc. 2003, 125, 11508.
15. Kina, A.; Ueyama, K.; Hayashi, T. Org. Lett. 2005, 7, 5889.
16. Defieber, C.; Paquin, J. F.; Serna, S.; Carreira, E. Org. Lett. 2004, 6, 3873.
17. Feng, C. G.; Lin, G. Q.; Wang, Z. Q.; Xu, M. H. J. Am. Chem. Soc. 2007, 129, 5336.
18. Nishimura, T.; Kumamoto, H.; Nagaosa, M.; Hayashi, T. Chem. Commun., 2009, 38, 5713.
19. Feng, C. G.; Wang, Z. Q.; Shao, C.; Xu, M. H.; Lin, G. Q. Org. Lett. 2008, 10, 4101.
20. Brown, M. K.; Corey, E. J. Org. Lett. 2010, 12, 172.
21. Shao, C.; Yu, H. J.; Wu, N. Y.; Feng, C. G.; Lin, G. Q. Org. Lett. 2010, 12, 3820.
22. Wang, Z. Q.; Feng, C. G.; Zhang, S. S.; Xu, M. H.; Lin, G. Q. Angew. Chem. Int. Ed. 2010, 49, 5780.
23. Molander, G. A.; Biolatto, B. J. Org. Chem. 2003, 68, 4302.
24. Angelina, F. P.; Dora, M. G. A.; Ysbrain, J. G. V.; Armando, A. C.; Rosalinda, C. J. Org. Chem. 1992, 57, 6067.
25. Drakulić, B. J.; Stanojković, T. P.; Žižak, Ž. S.; Dabović, M. M. Eur. J. Med. Chem. 2011, 46, 3265.