本論文係利用1-胺基-2-羥基-雙環[2.2.1]庚烷之衍生物作為掌性
配位基與硼烷•甲硫醚錯化物( BH3•SMe2 )結合形成掌性催化劑，對酮類進行不對稱催化還原反應。

在不對稱還原反應中，發現鏡像選擇性受到掌性配位基種類、掌性配位基當量數、溫度、受質等因素影響；此反應的最佳條件為：使用0.1毫莫耳的掌性配位基14及1.1毫莫耳的硼烷•甲硫醚，以2毫升的四氫呋喃為溶劑溶解，在60℃下攪拌30分鐘後，再將1毫莫耳的酮類溶於2毫升的四氫呋喃中，緩慢滴加1小時，進行不對稱催化還原反應，即可產生具光學活性的二級醇，並誘導出高達92%的鏡像選擇性。

This thesis dealt with the catalytic asymmetric borane reduction of prochiral ketones using in situ generated oxazaborolidine derived from (1S,2R,4R)-1-amino-7,7-dimethyl-bicyclo[2.2.1]heptan-2-ol.
In the asymmetric reduction, we found the factors which affected the enantioselectivity including the structure and the loading amount of catalyst, the reduction temperature, the substrate, etc. The best experimental conditions found for the asymmetric reduction requires the use of 10 mol% of catalyst, prepared by stirring 0.1eq 1,2-amino alcohol 14 with 1.1eq BH3•SMe2 in THF at 60oC for 0.5hr, followed by dropwise addition of the substrate at the same temperature. Optically active secondary alcohols were obtained in good chemical yields and up to 92% ee.

參 考 文 獻
1. Burkhardt, E. R.; Matos, K. Chem. Rev. 2006, 106, 2617.
2.Chandrasekhar, S.; Reddy, M. V. Tetrahedron 2000, 56, 6339
3.Keen, S. P.; Cowden, C. J.; Bishop, B. C.; Brands, K. M.; Davies, A. J.; Dolling, U. H.; Lieberman, D. R.; Stewart, G. W. J. Org. Chem. 2005, 70, 1771.
4.Bode J. W.; Carreira, E. M. J. Org. Chem. 2001, 66, 6410.
5.Brands, K. M. J.; Payack, J. F.; Rosen, J. D.; Nelson, T. D.; Candelario, A.; Huffman, M. A.; Zhao, M. M.; Li, J.; Craig, B.; Song, Z. J.; Tschaen, D. M.; Hansen, K.; Devine, P. N.; Pye, P. J.; Rossen, K.; Dormer, P. G.; Reamer, R. A.; Welch, C. J.; Mathre, D. J.; Tsou, N. N.; McNamara, J. M.; Reider, P. J. J. Am. Chem Soc. 2003, 125, 2129.
6.Chen, F. E.; Yuan, J.-L.; Dai, H.-F.; Kuang, Y.-Y.; Chu, Y. Synthesis 2003, 14, 2155.
7.Ross Kelly, T.; Whiting, A,; Chandrakumar, N. S. J. Am. Chem. Soc. 1986, 108, 3510.
8.Corey, E. J.; Loh, T-P. J. Am. Chem. Soc. 1991, 113, 8966.
9.Parmee, E. R.; Tempkin, O.; Masamune, S. J. Am. Chem. Soc. 1991, 113, 9365.
10.Joshi, N. N.; Srebnik, M.; Brown, H. C. Tetrahedron Lett. 1989, 30, 5551.
11.傅怡評，清華大學化學系九十五年度博士論文。
12.林揚閔，清華大學化學系八十九年度碩士論文。
13.Itsuno, S.; Ito, K.; Hirao, A.; Nakahama, S. J. Chem. Soc., Chem.Commun. 1983, 469.
14.Corey, E. J.; Bakshi, R. K.; Shibata, S. J. Am. Chem. Soc. 1987, 109, 5551.
15.Corey, E. J.; Bakshi, R. K.;Shibata, S.; Chen, C. P.; Singh, V. K. J. Am. Chem. Soc. 1987, 109, 7925.
16.Prasad, K. R. K.; Joshi, N. N. Tetrahedron: Asymmetry 1996, 7, 3147.
17.Demir, A. S.; Mecitoglu, I.; Tanyeli, C.; Gulbeyaz, V. Tetrahedron: Asymmetry 1996, 7, 3359.
18.Fiaud, J. C.; Maze, F.; Kagan, H. B. Tetrahedron:
Asymmetry 1998, 9, 3647.
19.Li, X.; Yeung, C. H.; Chan, A. S. C.; Yang, T. K Tetrahedron: Asymmetry 1999, 10, 759.
20.Santhi, V.; Rao, J. M. Tetrahedron: Asymmetry 2000, 11, 3553.
21.Zou, H.-H.; Hu, J.; Zhang, J.; You, J.-S.; Ma, D.; Lü , D.; Xie, R.-G. J. Mol. Catal. A 2005, 242, 57.
22.Lapis, A. A. M.; Fatima, A. D.; Martins, J. E. D.; Costa, V. E. U.; Pilli, R. A.Tetrahedron Lett. 2005, 46, 495.
23.Hu, J.-B.; Zhao, G.; Yang, G.-S.; Ding, Z.-D. J. Org. Chem. 2001, 66, 303.
24.Dalicsek, Z.; Pollreisz, F.; Gömöry, Á.; SoÓs, T. Org. Lett. 2005, 7, 3243.
25.Stepanenko, V.; Jesús, M. D.; Correa, W.; Guzmán, I.; Vázquez, C.; Cruz, W.; Ortiz-Marciales, M.; Barnes, C. L. Tetrahedron Lett. 2007, 48, 5799.
26.Kuhn, H.; Lanham, K.; Braslau, R. Tetrahedron Lett. 1996, 37, 7933.
27.黃全德博士論文，國立清華大學化學系，1999年。
28.Mathre, D. J.; Thompson, A. S.; Douglas, A. W.; Hoogsteen, K.; Carroll, J. D.; Corley, E. G.; Grabowski, E. J. J. J. Org. Chem. 1993, 58, 2880.
29.Xu, J.; Wei, T.; Zhang, Q. J.Org. Chem. 2003, 68, 10146.
30.Xu, J.; Wei, T.; Lin, S.; Zhang, Q. Helv. Chim. Acta. 2005, 88,180.
31.Corey, E. J.; Helal, C. J. Angew. Chem., Int. Ed. 1998, 37, 1987.
32.Cai, D.W.; Tschaen, D. M.; Shi, Y. J.; Verhoeven, T. R.; Reamer, R. A.; Douglas, A. W. Tetrahedron Lett. 1993, 34, 3243.
33.Abdel-Magid, A. F.; Carson, K. G.; Harris, B. D.; Maryanoff, C. A. J. Org. Chem. 1996, 61, 3849.
34.Oppolzer, W.; Radinov, R. N. Tetrahedron Lett. 1988, 29, 5645.
35.Nakamura, K.; Matsuda, T. J. Org. Chem. 1998, 63, 8957.
36.Weber, B.; Seebach, D. Tetrahedron 1994, 50, 7473.
37.Mori, M.; Imma, H.; Nakai, T. Tetrahedron Lett. 1997, 38, 6229.
38.Palmer, M.; Walsgro, T.; Will, M. J. Org. Chem. 1997, 62, 5226.
39.Kotsuki, H.; Shimanouchi, T.; Ohshima, R.; Fujiwara,S. Tetrahedron 1998, 54, 2709.
40.Nishiyama, H.; Yamaguchi, S.; Park, S. B.; Itoh, K. Tetrahedron: Asymmetry 1993, 4, 143.