一連串由三牙配子N-3,5-取代基-，N-3,4-苯并-和N-5,6-苯并-亞柳-α-胺基酸所衍生之釩氧（IV）錯合物，可以有效分別扮演各式3-,6-,7-取代基-2-酚氧化偶合反應、硫氧化反應和Mukaiyama-type醛醇加成的催化角色。我們以2-羥基-1-苯并柳醛和2-胺基異戊酸（或苯丙胺酸）所衍生而成的氧釩（IV）錯合物為催化劑，可以得到1,1'-雙-酚，產率可達75~100%，和高達68%的鏡像選擇性。各類硫化物亦可經由本實驗室所開發之三牙配子氧釩錯合物來得到相對的硫氧化產物，初步以硫大茴香醚為起始物所做的研究顯示，5 mol%的催化量配合35%的H2O2水溶液在-20 oC下反應可得到62-97%的產率和最高65%的鏡像超越值。我們成功地減少硫化物的過氧化現象（<2%），同時也維持了催化劑的反應活性。另外，我們以苯甲醛與γ-丁酸內酯所衍生之矽烷基半縮醛進行醛醇加成，在10 mol%催化量於-78 oC下反應48小時可以得到45-90%的產率，非鏡像立體選擇性則可達5/95（syn/anti），值得注意的是，在文獻中尚未發表此例的鏡像選擇性，而我們得到高達50%的鏡像超越值（for anti），此外再進一步擴大對芳香族醛類的研究，其初步的研究結果在此發表。

A series of chiral oxovanadium(IV) complexes derived from tridentate N-3,5-substituted and N-3,4-benzo- and N-5,6-benzo-salicylidene-α-amino acids can serve as efficient catalysts for the enantioselective oxidative couplings of various 3-,6-,7-substituted- 2-naphthols under O2 and oxidation of sulfides with H2O2 and Mukaiyama-type aldol additions. The best scenario involves the use of a vanadyl complex arising from 2-hydroxy-1-naphtholaldehyde and valine (or phenylalanine) in CCl4, leading to BINOLs in good yields (75-100%) and with enantioselectivities of up to 68%. Various sulfides can give corresponding sulfoxides by this catalytic reagent also. In case of thioansole, it can be performed with H2O2 (35%), a cheap and safe oxidant, as well as with 5 mol% vanadium catalyst at -20 oC. We are not only reduce the generation of sulfinate, but retain the catalytic reactivity. In addition, these type of vanadium complexes are utilized for Mukayaima additions between benzaldehyde and silyl ketene aectal (SKA) derived from γ-butyrolactone by 10 mol% catalyst at -78 oC in CH2Cl2 to afford aldol products in 45-90% yield with diastereoselectivities of up to 5/95 (syn/anti) and 50%ee (for anti). Remarkably, there were no reported about enantiomeric excess in this case before. On the other hand, four different aromatic aldehydes were also examined. We herein describe our preliminary finding.

中文摘要 I
英文摘要 II
第一章：N----亞柳胺基酸三牙配子衍生之氧釩錯合物在不對稱催化2-酚氧化偶合之研究 P1
第二章：N----亞柳胺基酸三牙配子衍生之氧釩錯合物在不對稱催化硫化物氧化反應之研究 P11
第三章：N----亞柳胺基酸三牙配子衍生之氧釩錯合物在不對稱催化Mukaiyama-type醛醇加成之研究 P19
第四章：氧釩錯合物紅外光振動光譜、旋光度值探討 P29
參考文獻 P31
第五章：實驗步驟和光譜數據
第壹節：分析儀器 P36
第貳節：藥品及純化方式 P38
第參節：實驗步驟及光譜數據 P40
附錄：
1H NMR 光譜圖
13C NMR 光譜圖
IR 光譜圖

參考文獻：
1. For recent reviews, see: (a) Kagan, H. B.; Riant, O. Chem. Rev. 1992, 92, 1007. (b) Mikami, K.; Shimizu, M. Chem. Rev. 1992, 92, 1021. (c) Pu, L. Chem. Rev. 1998, 98, 2405. (d) Noyori, R. Asymmetric Catalysis in Organic Synthesis; Wiley and Sons: New York, 1994. For leading references, see: (e) Kobayashi, S.; Komiyama, S.; Ishitani, H. Angew. Chem., Int. Ed. 1998, 37, 979. (f) Ishihara, K.; Nakamura, H.; Yamamoto, H. J. Am. Chem. Soc. 1999, 121, 7720.
2. (a) Noyori, R. Chem. Soc. Rev. 1989, 18, 187. (b) Noyori, R.; Takaya, H. Acc. Chem. Res. 1990, 23, 345.
3. (a) Feringa, B.; Wynberg, H. Bioorg. Chem. 1978, 7, 397. (b) Kawashima, M.; Hirata, R. Bull. Chem. Soc. Jpn. 1993, 66, 2002.
4. Toda, F.; Tanaka, K. J. Org. Chem. 1988, 53, 3607.
5. Miyano, S.; Kawahara, K.; Inoue, Y.; Hashimoto, H. Tetrahedron Lett. 1987, 355.
6. Pirkle, W. H.; Schreiner, J. L. J. Org. Chem. 1981, 46, 4988.
7. (a) Smrina, M.; Lorenc, M.; Hanu, V.; Sedmera, P.; Ko?ovsky, P. J. Org. Chem. 1992, 57, 1917. (b) Smrina, M.; Polakova, J.; Vyskoil, S.; Ko?ovsky, P. J. Org. Chem. 1993, 58, 4534. (c) Smrina, M.; Vyskoil, S.; Maa, B.; Polaek, M.; Claxton, T. A.; Abbott, A. P.; Ko?ovsky, P. J. Org. Chem. 1994, 59, 2156. (d) Brussee, J.; Groenendijk, J. L. G.; te Kopple, J. M.; Jansen, A. C. A. Tetrahedron 1985, 16, 3313.
8. Osa, T.; Kashiwagi, Y.; Yanagisawa, Y.; Bobbitt, J. M. J. Chem. Soc., Chem. Commun. 1994, 2535.
9. (a) Nakajima, M.; Miyoshi, I.; Kanayama, K.; Hashimoto, S.-I.; Noji, M.; Koga, K. J. Org. Chem. 1999, 64, 2264 and references therein. (b) A catalytic cross-coupling protocol with a CuCl2-sparteine-AgCl based system was first demonstrated by Smrina and Ko?ovsky (ref 7b).
10. Li, X.; Kozlowski, M. C. Org. Lett. 2001, 3, 1137.
11. (a) Nakajima, K.; Kojimo, M.; Fujita, J. Chem. Lett. 1986, 1483. (b) Takai, T.; Yamada, T.; Mukaiyama, T. Chem. Lett. 1990, 1657. (c) Bolm, C.; Bienewald, F. Angew. Chem., Int. Ed. Engl. 1995, 34, 2640.
12. (a) Dichmann, K.; Hamer, G.; Nyburg, S. C.; Reynold, S. W. F. J. Chem. Soc. D 1970, 1295. (b) For DMSO complexes, see: Agarwal, K.; Singh, G. J. Indian Chem. Soc. 1986, 63, 926.
13. Chen, C.-T.; Hon, S.-W.; Weng, S.-S. Synlett 1999, 816.
14. Hwang, D. R.; Chen, C. P.; Uang, B. J. J. Chem. Soc. Chem. Commun. 1999, 1207.
15. (a) Evans, D. A.; Burgey, C. S.; Kozlowski, M. C.; Tregay, S. W. J. Am. Chem. Soc. 1999, 121, 686 and references therein. (b) Nishiyama, H.; Kondo, M.; Nakamura, T.; Itoh, K. Organometallics 1991, 10, 500.
16. (a) Kiyooka, S.-I.; Kaneko, Y.; Komura, M.; Matsuo, H.; Nakano, M. J. Org. Chem. 1991, 56, 2276. (b) Parmee, E. R.; Tempkin, O.; Masamune, S. J. Am. Chem. Soc. 1991, 113, 9365. (c) Corey, E. J.; Cywin, C. L.; Roper, T. D. Tetrahedron Lett. 1992, 33, 6907.
17. (a) Annis, D. A.; Jacobsen, E. N. J. Am. Chem. Soc. 1999, 121, 4147. (b) Zhang, W.; Jacobsen, E. N. J. Org. Chem. 1991, 56, 2296.
18. Theriot, L. J.; Carlisle, G. O.; Hu, H. J. J. Inorg. Chem. 1969, 31, 2841.
19. 詳見實驗數據目錄
20. Cogan, D. A.; Liu, G.; Kim, K.; Backes, B. J.; Ellman, J. A. J. Am. Chem. Soc. 1998, 120, 8011.
21. Defined as (%R - %S/%R + %S) × 100.
22. 幾乎在所有的例子中，所得到的結晶固體為消旋的產物，不過，我們將母液濃縮以後所得到的產物具100%的光學純度。
23. Carreno M. C., Chem. Rev. 1995, 95, 1717.
24. (a) Andersen, K. K. Tetrahedron Lett. 1962, 18, 93. (b) Andersen, K. K.; Gaffield, W.; Papanikolaou, N. E.; Foley, J. W.; Perkin, R. I. J. Am. Chem. Soc. 1964, 88, 5637.
25. (a) Colonna S.; Gaggero, N.; Casella, L.; Gasella, N.; Carrea, G.; Pasta, P. Teteahedron 1992, 3, 95. (b) Fu, H.; Kondo, H.; Ichikawa, Y.; Look, G. C.; Wong, C.-H. J. Org. Chem. 1992, 57, 7265.
26. (a) Brunel, J.-M.; Kagan, H. B. Bull. Soc. Chem. Fr. 1996, 133, 1109. (b) Colonna, S.; Manfredi, A.; Spadoni, M.; Casella, L.; Gullotti, M. J. Chem. Soc., Perkin Trans. I 1987, 71. (c) Sasaki, C.; Nakajima, K.; Kojima, M.; Fujita, J. Bull. Chem. Soc. Jpn. 1991, 64, 1318. (d) Furia, F. Di.; Licini, G.; Modena, G.; Motterle, R. J. Org. Chem. 1996, 61, 5175.
27. (a) Palucki, M.; Hanson, P.; Jacobsen, E. N. Terahedron Lett. 1992, 33, 7111. (b) Noda, K.; Hosoya, N.; Irie, R.; Yamashita, Y.; Katsuki, T. Tetrahedron 1994, 50, 9609. (c) Nagata, T.; Imagawy, K.; Yamada, T.; Mukaiyama, T. Bull. Chem. Soc. Jpn. 1995, 68, 3241. (d) Halterman, R. L.; Jan, S,-T.; Nimmons, H. L.; Standlee, D. J.; Khan, M. A. Tetrahedron 1997, 53, 11257.
28. Nakajima, K.; Kojima, M.; Toriumi, K.; Saito, K.; Fujita, J.; Bull. Chem. Soc. Jpn. 1989, 62, 760.
29. (a) Bolm, C.; Bienewald, F. Angew. Chem. Int. Ed. Engl. 1995, 34, 2640. (b) Bolm, C.; Bienewald, F. Synlett 1998, 1327. (c) Cogan, D. A.; Liu, G.; Kim, K.; Backes, B. J.; Ellman, J. A. J. Am. Chem. Soc. 1998, 120, 8011.
30. Hon, S.-W.; Li C.-H.; Kuo, J.-H.; Barhate, N. B.; Liu, Y.-H.; Wang, Y.; Chen, C.-T. Org. Lett. 2001, 3, 869.
31. (a) Masamune, S.; Sato, T.; Kim, B. M.; Wollmann, T. A. J. Am. Chem. Soc. 1986, 108, 8279. (b) Corey, E. J.; Kim, S. S. J. Am. Chem. Soc. 1990, 112, 4976.
32. Mukaiyama, T. Aldrichimica Acta 1996, 29, 59.
33. (a) Heathcock, C. H. Science 1981, 214, 395. (b) Evans, D. A.; Takacs, J. M.; McGee, L. R.; Ennis, M. D.; Mathre, D. J.; Bartroli, J. Pure Appl. Chem. 1981, 53, 1109. (c) Masamune, S.; Choy, W.; Petersen, J. S.; Sita, L. R. Angew. Chem. Int. Ed. Engl. 1985, 24, 1.
34. (a) Siegel, C.; Thorton, E. R. J. Am. Chem. Soc. 1989, 111, 5722. (b) Evans, D. A.; McGee, L. R. J. Am. Chem. Soc. 1981, 103, 2876.
35. Eliel, E. L.; Wilen, S. H. Stereochemistry of Organic Compounds; Wily: New York, 1994; 835.
36. (a) Kobayashi, S.; Hachiya, I.; Ishitani, H.; Arki, M. Synlett 1993, 472. (b) For rare earth metal complexes, see: Kobayashi, S. Synlett 1994, 689.
37. (a) Hollis, T. K.; Bosnich, B. J. Am. Chem. Soc. 1995, 117, 4570. (b) Carreira, E. M.; Singer, R. A. Tetrahedron Lett. 1994, 35, 4323.
38. Mukaiyama, T.; Akamatsu, H.; Han, J. S. Chem. Lett. 1990, 889.
39. (a) Bach, T.; Fox, D. N. J. Chem. Soc. Chem. Commun. 1992, 1634. (b) Colombo, L.; Ulgheri, F. Tetrahedron Lett. 1989, 30, 6435.
40. Kobayashi, S.; Busujima, T.; Nagayama, S. Tetrahedron Lett. 1998, 39, 1579.
41. (a) Evans, D. A.; Murry, J. A.; Kozlowski, M. C. J. Am. Chem Soc. 1996, 118, 5814. (b) Evans, D. A.; Kozlowski, M. C.; Burgey, C. S.; MacMillan, D. W. C. J. Am. Chem. Soc. 1997, 119, 7893.
42. (a) For a review of vanadium in synthesis, see: Hirao, T. Chem. Rev. 1997, 97, 2707. (b) For the only documented example on the use of V(IV) in asymmetric Diels-Alder reation, see: Togni, A. Organometallics 1990, 9, 3106. (c) Togni, A.; Rist, G.; Rihs, G.; Schweiger, A. J. Am. Chem. Soc. 1993, 115, 1908.
43. (a) Nakajima, K.; Kojimo, M.; Fujita, J. Chem. Lett. 1986, 1483. (b) Takai, T.; Yamada, T.; Mukaiyama, T. Chem. Lett. 1990, 1657. (c) Bolm, C.; Bienewald, F. Angew. Chem. Int. Ed. Engl. 1995, 34, 2640.
44. For a general reiew: (a) Hirao, T. Chem. Rew. 1997, 97, 2707. (b) For oxidative couplings: Hwang, D. R.; Chen, C. P.; Uang, B. J. J. Chem. Soc. Chem. Commun. 1999, 1207. (c) For vicinal dialkylation of cyclic enones: Hirao, T.; Takada, T; Sakurai, H. Org. Lett. 2000, 2, 3659.
45. For recent application, see: (a) Belokon, Y.; North, M.; parsons, T. Org. Lett. 2000, 2, 1617. (b) Ishii, Y.; Matsunaka, K.; Sakaguchi, S. J. Am. Chem. Soc. 2000, 122, 7390.
46. Togni, A. Organomtetallics 1990, 9, 3106.
47. (a) Dichmann, K.; Hamer, G.; Nyburg, S. C.; Reynold, S. W. F. J. Chem. Soc. D. 1970, 1295. (b) For DMSO complexes, see: Agarwal, K.; Singh, G. J. Ind. Chem. Soc. 1986, 63, 926.
48. Vilas Boas, L.; Costa Pessoa, J. In Comprehensive Coordination Chemistry; Wilkinson, G.; Gillard, R. D.; McCleverty, J. A.; Eds. Pergamon: Oxoford, England, 1987, Vol. 3, p453.
49. (a) Hara, R.; Mukaiyama, T. Chem. Lett. 1989, 1909. (b) Mukaiyama, T.; Hara, R. Chem. Lett. 1989, 1171. (c) Mukaiyama, T.; Inubushi, A.; Suda, S.; Hara, R.; Kobayashi, S. Chem. Lett. 1990. 1015. (d) Kobayashi, S.; Suda, S.; Yamada, M.; Mukaiyama, T. Chem. Lett. 1994, 97.
50. Selbin, J. Chem. Rev. 1965, 65, 153.