摘要
我們發現了新的金銀催化劑所產生的催化系統，利用軟性的炔類與金屬偶和可建構出高立體選擇性、高轉換率的碳環或雜環化合物，且伴隨著溫和的反應條件與良好的官能基容忍度，一系列的反應將於以下四章節做介紹。

第一章利用金催化劑與1-oxo-4-oxy-5-ynes進行催化反應而得到高立體選擇性的產物9-oxabicyclo[3.3.1]nona-4,7-dienes。首例利用s-trans-methylene(vinyl)oxonium化合物進行1,4-dipolar [4+2]環化反應成高度立障的 anti-Bredt 氮氧環。

第二章利用銀催化劑使得化合物1-tosylhydrazon-4-oxy-5-ynes進行骨牌式的6-exo-dig-azacyclization與[3+2]環化加成反應。這種新的氮環合成反應有相當廣泛的應用性。

第三章為第一個成功的利用8-methylquinoline oxide與金催化劑對3-en-1-ynes進行氧化加成氧化反應。這可以廣泛的應用在benzenoid 與非benzenoid的起始物上，而得到indanone與cyclopentenone類化合物。

第四章利用金催化劑催化1,7烯炔與酮類得到[2+2+2]環化加成產物，從實驗資料顯示，此反應會先經過含酮四環金金屬中間體而得。

Refrences
1. See reviews: (a) Nicolaou, K. C.; Snyder, S. A.; Montagnon, T.; Vassilikogiannakis, G. Angew.
Chem., Int. Ed. 2002, 41, 1668. (b) Pindur, U.; Lutz, G.; Otto, C. Chem. Rev. 1993, 93, 741. (c) Boger,
D. L. Chem. Rev. 1986, 86, 781. (d) Boger, D. L. J. Heterocyclic Chem. 1996, 33, 1519. (e) Boger, D.
L. Tetrahedron 1983, 39, 2869. (f) Trost, B. M. Acc. Chem. Res. 2002, 35, 695. (g) Trost, B. M.
Angew. Chem. 1995, 107, 285; Angew. Chem. Int. Ed. Engl. 1995, 34, 259. (h) Trost, B. M. Science.
1991, 254, 1471.
2. (a) Anastas, P.; Warner, J. C. in Green Chemistry, Theory and Practice, Oxford University Press,
Oxford, 1998. (b) Anastas, P.T.; Kirchhoff, M. M. Acc. Chem. Res. 2002, 35, 686. (c) Anastas, P. T.;
Zimmerman, J. B.; Environ. Sci. Technol. 2003, 37, 94A. (d) Poliakoff, M.; Fitzpatrick, J. M.; Farren,
T. R.; Anastas, P. T. Science. 2002, 297, 807. (e) Trost, B. M.; Toste, D. F.; Pinkerton, A. B. Chem.
Rev. 2001, 101, 2067.
3. (a) Janssen, E. M.W.; Folmer, J. C. W.; Wiegers, G. A. J. Less-Common Met. 1974, 38, 71 –76. (b)
Vogler, A.; Kunkely, H.; Coord. Chem. Rev. 2001, 219–221, 489 – 507. (c) Hashmi, A. S. K.; Blanco,
M. C.; Fischer, D.; Bats, J. W. Eur. J. Org. Chem. 2006, 1387 – 1389.
4. (a) Iwasawa, N.; Shido, M.; Kusama, H. J. Am. Chem. Soc. 2001, 123, 5814 – 5815. (b) Kusama, H.;
Takaya, J.; Iwasawa, N. J. Am. Chem. Soc. 2002, 124, 11592 – 11593. (c) Kusama, H.; Funami, H.;
Takaya, J.; Iwasawa, N. Org. Lett. 2004, 6, 605 – 608. (d) Takaya, J.; Kusama, H.; Iwasawa, N.; Chem.
Chapter I
36
Lett. 2004, 33, 16–17. (e) Kusama, H.; Funami, H.; Shido, M.; Hara, Y.; Takaya, J.; Iwasawa, N. J. Am. Chem. Soc. 2005, 127, 2709 – 2716. (f) Kusama, H.; Miyashita, Y.; Takaya, J.; Iwasawa, N. Org. Lett. 2006, 8, 289 – 292. (g) Kusama, H.; Suzuki, Y.; Takaya, J.; Iwasawa, N. Org. Lett. 2006, 8, 895 – 897. (h) Kusama, H.; Funami, H.; Iwasawa, N. Synthesis. 2007, 2014 – 2024.
5. (a) Asao, N.; Takahashi, K.; Lee, S.; Kasahara, T.; Yamamoto, Y. J. Am. Chem. Soc. 2002, 124, 12650 – 12651; (b) Asao, N.; Nogami, T.; Lee, S.; Yamamoto, Y. J. Am. Chem. Soc. 2003, 125, 10921 – 10925. (c) Asao, N.; Kasahara, T.; Yamamoto, Y. Angew. Chem. 2003, 115, 3628 – 3630; Angew. Chem. Int. Ed. 2003, 42, 3504 – 3506. (d) Asao, N.; Aikawa, H.; Yamamoto, Y. J. Am. Chem. Soc. 2004, 126, 7458 – 7459. (e) Asao, N.; Sato, K.; Menggenbateer.; Yamamoto, Y. J. Org. Chem. 2005, 70, 3682 – 3685. (f) Asao, N.; Aikawa, H. J. Org. Chem. 2006, 71, 5249 – 5253. (g) Asao, N.; Sato, K. Org. Lett. 2006, 8, 5361 – 5363. (h) Shin, S.; Gupta, A. K.; Rhim, C. Y.; Oh, C. H. Chem. Commun. 2005, 4429 – 4431. (i) Kim, N.; Kim, Y.; Park, W.; Sung, D.; Gupta, A. K.; Oh, C. H. Org. Lett. 2005, 7, 5289 – 5291. (j) Gupta, A. K.; Rhim, C. Y.; Oh, C. H.; Mane, R. S.; Han, S.-H. Green Chem. 2006, 8, 25 – 28. (k) Dyker, G.; Hildebrandt, D. J. Org. Chem. 2005, 70, 6093 – 6096. (l) Hildebrandt, D.; Hggenberg, W.; Kanthak, M.; PlIger, T.; MHller, I. M.; Dyker, G. Chem. Commun. 2006, 2260 – 2261. (m) Oh, C. H.; Ryu, J. H.; Lee, H. I. Synlett. 2007, 2337 – 2342. (n) Zhu, J.; Germain, A. R.; Porco, J. A. ; Jr. Angew. Chem. 2004, 116, 1259 – 1263; Angew. Chem. Int. Ed. 2004, 43, 1239 – 1243. (o) Beeler, A. B.; Su, S.; Singleton, C. A.; Porco, J. A.; Jr. J. Am. Chem. Soc. 2007, 129, 1413 – 1419.
6. (a) Patil, N. T.; Wu, H.; Yamamoto, Y. J. Org. Chem. 2005, 70, 4531 – 4534. (b) Asao, N.; Yudha, S.; Nogami, T.; Yamamoto, Y. Angew. Chem. 2005, 117, 5662 – 5664; Angew. Chem. Int. Ed. 2005, 44, 5526 – 5528. (c) Yao, X.; Li, C.-J. Org. Lett. 2006, 8, 1953 – 1955. (d) Yanada, R.; Obika, S.; Kono, H.; Takemoto, Y. Angew. Chem. 2006, 118, 3906 – 3909; Angew. Chem. Int. Ed. 2006, 45, 3822 – 3825. (e) Zhang, J.; Schmalz, H.-G. Angew. Chem. 2006, 118, 6856 – 6859; Angew. Chem. Int. Ed. 2006, 45, 6704 – 6707. (f) Oh, C. H.; Reddy, R.; Kim, A.; Rhim, C. Y. Tetrahedron Lett. 2006, 47, 5307 – 5310. (g) Liang, Y.; Xie, Y.-X.; Li, J.-H. Synthesis. 2007, 400 – 406.
7. (a) Kusama, H.; Iwasawa, N. Chem. Lett. 2006, 35, 1082 – 1087. (b) Asao, N. Synlett. 2006, 1645 – 1656.
8. Miki, K.; Uemura, S.; Ohe, K. Chem. Lett. 2005, 34, 1068 – 1073.
9. Miura, T.; Murakami, M. Chem. Commun. 2007, 217.
10. Tovar, R.; Swager, T. M. J. Org. Chem. 1999, 64, 6499 – 6504.
11. Numata, A.; Kondo, Y.; Sakamoto, T. Synthesis. 1999, 306 – 311.
Chapter I
37
12. Huang, Q.; Hunter, J. A.; Larock, R. C. J. Org. Chem. 2002, 67, 3437 – 3444, and references therein.
13. (a) Roesch, K. R.; Larock, R. C. J. Org. Chem. 2002, 67, 86. (b) Dai, G.; Larock, R. C. Org. Lett. 2001, 3, 4035. (c) Huang, Q.; Larock, R. C. J. Org. Chem. 2003, 68, 980 and references therein. (d) Ohtaka, M.; Nakamura, H.; Yamamoto, Y. Tetrahedron Lett. 2004, 45, 7339. (e) The palladium-catalyzed cyclization of related acetals leads to indenol ethers: Nakamura, I.; Gabajracharya, G. B.; Mizushima, Y.; Yamamoto, Y. Angew. Chem. 2002, 114, 4504 – 4507; Angew. Chem. Int. Ed. 2002, 41, 4328 – 4331.
14. (a) Iritani, K.; Matsubara, S.; Utimoto, K. Tetrahedron Lett. 1988, 29, 1799. (b) Arcadi, A.; Cacchi, S.; Marinelli, F. Tetrahedron Lett. 1989, 30, 2581. (c) Cacchi, S.; Fabrizi, G.; Pace, P. J. Org. Chem. 1998, 63, 1001. (d) Kamijo, S.; Yamamoto, Y. J. Org. Chem. 2003, 68, 4764. (e) Ezquerra, J.; Pedregal, C.; Lamas, C. J. Org. Chem. 1996, 61, 5804. (f) Hiroya, K.; Itoh, S.; Sakamoto, T. J. Org. Chem. 2004, 69, 1126 and references therein. (g) Larock, R. C.; Harrison, L. W. J. Am. Chem. Soc. 1984, 106, 4218.
15. (a) Torii, S.; Xu, L. H.; Okumoto, H. Synlett 1992, 515. (b) Lu¨tjens, H.; Scammells, P. J. Synlett 1999, 1079. (c) Hu, Y.; Yang, Z. Org. Lett. 2001, 3, 1387. (d) Houpis, I. N.; Choi, W. B.; Reider, P. J.; Molina, A.; Churchill, H.; Lynch, J.; Volante, R. P. Tetrahedron Lett. 1994, 35, 9355. (e) Nan, Y.; Miao, H.; Yang, Z. Org. Lett. 2000, 2, 297 and references therein.
16. (a) Bellina, F.; Ciucci, D.; Vergamini, P.; Rossi, R. Tetrahedron 2000, 56, 2533 and references therein. (b) Sakamoto, T.; An-naka, M.; Kondo, Y.; Yamanaka, H. Chem. Pharm. Bull. 1986, 34, 2754. (c) Sashida, H.; Kawamukai, A. Synthesis 1999, 1145.
17. G. Dyker, W. Stirner, G. Henkel, M. KJckerling, Tetrahedron Lett. 1999, 40, 7457 – 7458.
18. (a) Asao, N.; Shimada, T.; Shimada, T.; Yamamoto, Y. J. Am. Chem. Soc. 2001, 123, 10899-10902. (b) Asao, N.; Yamamoto, Y. Bull. Chem. Soc. Jpn. 2000, 73, 1071-1087 and references therein.
19. Kuznetsov, E.; Shcherbakova, I. V.; Balaban, A. T. AdV. Heterocycl. Chem. 1990, 50, 157-254.
20. Straub, B. F. Chem. Commun. 2004, 1726 – 1728.
21. Kim, N.; Kim, Y.; Park, W.; Sung, D.; Gupta, A. K.; Oh, C. H. Org. Lett. 2005, 7, 5289 – 5291.
22. Kusama, H.; Funami, H.; Takaya, J.; Iwasawa, N. Org. Lett. 2004, 6, 605 – 608.
23. (a) Pape, A. R.; Kaliappan, K. P.; Küdig, E. P. Chem. Rev. 2000, 100, 2917 – 2940. (b) Rawson, D. J.; Meyers, A. I. J. Org. Chem. 1991, 56, 2292 – 2294. (c) Meyers, A. I.; Brown, J. D. Tetrahedron
Chapter I
38
Lett. 1987, 28, 5279 – 5282. (d) Meyers, A. I.; Lutomski, K. A.; Laucher, D. Tetrahedron. 1988, 44, 3107 – 3118. (e) Amurrio, D.; Khan, K.; KCndig, E. P. J. Org. Chem. 1996, 61, 2258 – 2259, and references therein. (f) Ahmed, A.; Clayden, J.; Rowley, M. Chem. Commun. 1998, 297 – 298. (g) Tomioka, K.; Shindo, M.; Koga, K. Tetrahedron Lett. 1990, 31, 1739 – 1740. (h) omioka, K.; Inoue, T. I.; Shindo, M.; Koga, K. Tetrahedron Lett. 1990, 31, 6681 – 6684. (i) Shindo, M.; Koga, K.; Asano, Y.; Tomioka, K. Tetrahedron. 1999, 55, 4955 – 4968. (j) Tomioka, K.; Shindo, M.; Koga, K.; J. Am. Chem. Soc. 1989, 111, 8266 – 8268.
20. (a) Danheiser, R. L.; Gould, A. E.; Fernandez, de la Predilla, R.; Helgason, A. L. J. Org. Chem. 1994, 59, 5514-5515. (b) Bradley, A. Z.; Johnson, R. P. J. Am. Chem. Soc. 1997, 119, 9917-9918.
24. Kusama, H.; Ishida, K.; Funami, H.; Iwasawa, N. Angew. Chem. Int. Ed. 2008, 47, 4903 –4905.
25. (a) Mehta, G.; Muthusamy, S.; Tetrahedron. 2002, 58, 9477 – 9504. (b) Padwa, A. Helv. Chim. Acta. 2005, 88, 1357 – 1374.
26. (a) Hall, H. K. JR. Chem. Rev. 1983, 83, 549-555. (b) Marshal1 J. A.; Faubl H. J. Am. Chem. Soc. 1970, 92, 948-955. (c) Tani, K.; Stoltz, B. M. Nature 2006, 441, 731–734.
27. (a) Houk, K. N.; Lin, Y.-T.; Brown, F. K. J. Am. Chem. Soc. 1986, 108, 554. (b) Goldstein, E.; Beno, B.; Houk, K. N. J. Am. Chem. Soc. 1996, 118, 6036.
28. The calculations were performed using the B3LYP method with the LANL2DZ basis set (B3LYP/LANL2DZ).
29. Reviews: (a) Patil, N. T.; Yamamoto, Y. Chem. Rev. 2008, 108, 3395. (b) Abu Sohel, S. Md.; Liu, R.-S. Chem. Soc. Rev. 2009, 38, 2269.
30. For s-cis-oxoniums I, their [4+2]-cycloaddition intermediates V will not give anti-Bredit’s oxacycles VI; these hypothetic intermediates undergo facile rearrangement to dihydronaphthalenes5a-b or 8-oxabicyclo[3.2.1]-octanes6. (a) Asao, N.; Kasahara, T.; Yamamoto, Y. Angew. Chem., Int. Ed. 2003, 42, 3504. (b) Asao, N.; Aikawa, H.; Yamamoto, Y. J. Am. Chem. Soc. 2004, 126, 7458. (c) Hsu, Y.-C.; Ting, C.-M.; Liu, R.-S. J. Am. Chem. Soc. 2009, 131, 2090. (d) Shu, X.-Z.; Zhao, S.-C.; Ji, K.-G.; Zheng, Z.-J.; Liu, X.-Y.; Liang, Y.-M. Eur. J. Org. Chem. 2009, 117.
31. For [3+2]-cycloadditions, see selected examples: (a) Kusama, H.; Ishida, K.; Funami, H.; Iwasawa, N. Angew. Chem., Int. Ed. 2008, 47, 4903. (b) Li, G.; Huang, X.; Zhang, L. J. Am. Chem. Soc. 2008,
Chapter I
39
130, 6944. (c) Oh, C. H.; Lee, J. H.; Lee, S. J.; Kim, J. I.; Hong, C. S. Angew. Chem., Int. Ed. 2008, 47, 7505. (d) Oh, C. H.; Lee, S. M.; Hong, C. S. Org. Lett. 2010, 12, 1308.
32. Other reactions for s-cis-oxonium I, see: (a) Liu, F.; Yu, Y.; Zhang, J. Angew. Chem., Int. Ed. 2009, 48, 5505. (b) Jin, T.; Yamamoto, Y. Org. Lett. 2007, 9, 5259. (c) Jin, T.; Yamamoto, Y. Org. Lett. 2008, 10, 3137.
33. Miki, K.; Uemura, S.; Ohe, K. Chem Lett. 2005, 34, 1068.
34. (a) Wünsch, B.; Zott, M.; Höfner, G. Arch. Pharm. 1992, 325, 733. (b) Wünsch, B.; Zott, M.;
Höfner, G. Arch. Pharm. 1992, 325, 823. (c) Maurin, C.; Bailly, F.; Cortelle, P. Curr.Med.Chem.
2003, 10, 1795. (d) Dupont, R.; Jeanson, L.; Mouscadet, J.-F.; Cotelle P. Bioorg. Med.Chem.
Lett. 2001, 11, 3175.
35. (a) Hashmi, A. S. K.; Schäfer, S.; Wölfle, M.; Gil, C. D.; Fischer, P.; Laguna, A.; Blanco, M.
C.; Gimeno, M. C. Angew. Chem., Int. Ed. 2007, 46, 6184. (b) Horino, Y.; Yamamoto, T.; Ueda
, K.; Kuroda, S.; Toste, F. D. J. Am. Chem. Soc. 2009, 131, 2809. (c) Cui, L.; Peng, Y.; Zhang, L.
J. Am. Chem. Soc. 2009, 131, 8394. (d) Bhunia, S.; Liu, R.-S. J. Am. Chem. Soc. 2008, 130,
16488. (e) Jime´nez- Nu´n˜ez, E.; Raducan, M .; Lauterbach, T.; Molawi, T.; Solorio, C. R.;
Echavarren, A. M. Angew. Chem., Int. Ed. 2009, 48, 6152.
36. For metal-allene bonding having the following dipolar character, see selected examples:(a) Kusama, H.; Ebisawa, M.; Funami, H.; Iwasawa, N. J. Am. Chem. Soc. 2009, 131, 16352. (b) Lee, J. H.; Toste, F. D. Angew. Chem. Int. Ed. 2007, 46, 912. (c) Lemiere, G.; Gandon, V.; Cariou, K.; Hours, A.; Fukuyama, T.; Dhimane, A.-L.; Fensterbank, L.; Malacria, M. J. Am. Chem. Soc. 2009, 131, 2993.
37. Asao, N.; Chan, C.-S.; Takahashi, K.; Yamamoto, Y. Tetrahedron, 2005, 61, 11322.
38. (a) Asao, N.; Nogami, T.; Takahashi, K.; Yamamoto, Y. J. Am. Chem. Soc. 2002, 124, 764–765. (b) Mondal, S.; Nogami, T.; Asao, N.; Yamamoto, Y. J. Org. Chem. 2003, 68, 9496–9498. (c) Patil, N. T.; Yamamoto, Y. J. Org. Chem. 2004, 69, 5139–5142. (d) Barluenga, J.; Vázquez-Villa, H.; Ballesteros,
Chapter I
40
A.; González, J. M. J. Am. Chem. Soc. 2003, 125, 9028–9029. (e) Yue, D.; Cá, N. D.; Larock, R. C.
Org. Lett. 2004, 6, 1581–1584.
39. (a) Chabaud, L.; James, P.; Landais, Y. Eur. J. Org. Chem. 2004, 3173. (b) Masse, C. E.; Panek, J.
S. Chem. Rev. 1995, 95, 1293.
40. (a) Knolker, H. J.; Foitzik, N.; Gabler, C.; Graf, R. Synthesis 1999, 145-151. (b) Knolker, H. J. J.
Prakt. Chem. 1997, 339, 304. (c) Danheiser, R. L.; Dixon, B. R.; Gleason, R. W. J. Org. Chem. 1992,
57, 6094. (d) Panek, J. S.; Yang, M. J. Am. Chem. Soc. 1991, 113, 9868.
41. (a) Tinsley, J. M.; Roush, W. R. J. Am. Chem. Soc. 2005, 127, 10818. (b) Angle, S. R.; El-Said, N.
A. J. Am. Chem. Soc. 2002, 124, 3608.
42. Angle, S. R.; El-Said, N. A. J. Am. Chem. Soc. 1999, 121, 10211.
43. For internal alkyne 9a, we observed a distinct 7-endo-dig cyclization to give indenyl ketone 10a in
45 % yield. Steric interaction between gold and n-butyl destabilizes intermediate II’. For the acetoxy
derivative 9b, we obtained 10b stereoselectively frofrom an initial 1,3-acetoxy shift followed by a [4+2]-
cycloaddition on benzopyrilium (see ref. 38).
44. Teng, T.-M.; Liu, R.-S. J. Am. Chem. Soc. 2010, 132, 9298.