本論文的研究主要是使用本實驗室所開發的掌性雙環 [2.2.1] 雙烯配基L1C與五莫耳百分率的一價銠金屬催化劑 (5 mol% of Rhodium) ，對苯並環丁醇 (Benzocyclobutenol) 進行選擇性開環，再與重氮酯 (Diazoester) 形成銠碳烯 (Rhodium carbene) 、並進行碳烯插入 (Carbene insertion) 反應得到銠烯醇鹽離子 (Rhodium enolate) ，接著進行分子內醛醇反應 (Intramolecular Aldol reaction) 得到具有連續兩個立體中心的茚醇 (Indanol) 化合物。反應在60 °C、以甲苯為溶劑的反應條件，並根據其不同的反應基質可得到高達82%的產率以及高達95% ee的鏡像超越值。

In this thesis, a Rh(I)-catalyzed regioselective ring cleavage of benzocyclobutenols 7 followed by enantioselective rhodium carbene insertion with various diazoesters 8 , and subsequent intramolecular aldol reaction via the thus obtained rhodium enolates is described. This transformation proceeds at 60 °C, in the presence 5 mol% of Rh(I) / L1C catalyst, to offer the corresponding products possessing two contiguous quaternary stereo-centers with up to 82% yield, and 95% ee.

1. (a) Franks, M. E.; Macpherson, G. R.; Figg, W. D. The Lancet 2004, 363, 1802. (b) Moghe, V. V.; Kulkarni, U.; Parmar, U. I. BombayHosp. J. 2008, 50, 472. (c) Landesman-Dwyer, S. Appl. Res. Ment.Retard. 1982, 3, 241. (d) Kelsey F. O. J. Dent. Res. 1967, 46, 1201.
2. (a) Heyman, M. B. Pediatrics. 2006, 118, 1279. (b) Enattah, N. S.; Sahi, T.; Savilahti, E.; Terwilliger, J. D.; Peltonen, L.; Järvelä, I. Nat. Genet. 2002, 30, 233. (c) Swallow, D. M.; Annu. Rev. Genet. 2003, 37, 197.
3. National Digestive Diseases Information Clearinghouse (NDDIC). NIDDK. [29 November 2011].
4. Cava, M. P.; Muth, K. J. Am. Chem. Soc. 1960, 82, 652.
5. Stevens, R. V.; Bisacchi, G. S. J. Org.Chem. 1982, 47, 2396.
6. Gokhale, A.; Schiess, P. Helv. Chim. Acta. 1998, 81, 251.
7. Rosa, D.; Chtchemelinine, A.; Orellana, A. Synthesis 2011, 76, 9157.
8. (a) Ishida, N.; Sawano, S.; Masuda, Y.; Murakami, M. J. Am. Chem. Soc. 2012, 134, 17502. (b) Ishida, N.; Ishikawa, N.; Sawano, S.; Masuda, Y.; Murakami, M. Chem. Commun. 2015, 51, 1882
9. (a) 林亞萱 (2016) Rhodium(I)-Catalyzed Regioselective Ring Opening of Benzocyclobutenol and Subsequent Conjugate Addition Reaction with Maleimides 碩士論文，國立台灣師範大學化學系，台北，台灣。 (b) 曾昊葳 博士研究成果
10. Xia, Y.; Liu, Z.; Liu, Z.; Ge, R.; Ye, F.; Hossain, M.; Zhang, Y.; Wang, J. J. Am. Chem. Soc. 2014, 136, 3013.
11. Yates, P. J. Am. Chem. Soc., 1952, 74, 5376.
12. Moriuti, S.; Takaya, H.; Noyori, R.; Nozaki, H. Tetrahedron Lett.
1966, 5239.
13. Paulissen, R.; Reimlinger, H.; Hayez, E.; Hubert, A.J. ; P. Teyssie.
Tetrahedron Lett. 1973, 14, 2233.
14. Ma, X; Jiang, J; Lv, S; Yao, W; Yang, Y.; Liu, S.; Xia, F.; Hu, W.
Angew. Chem. Int. Ed. 2014, 53, 13136.
15. Frisch, M. J. et al. Gaussian09, Rev.B.01; Gaussian, Inc., Wallingford,
2010.
16. (a) Lu, P.; Mailyan, A.; Gu, Z. et al. J. Am. Chem. Soc. 2014, 136, 17738. (b) Qiu, H.; Li, M.; Jiang L. Q. et al. Nat. Chem. 2012, 4, 733. (c) Xu, B.; Zhu, S. F.; Zuo, X. D.; Zhang, Z. C.; Zhou, Q. L. Angew. Chem. Int. Ed. 2014, 53, 3913. (d) Ren, L.; Lian, X. L.; Gong, L. Zhu. Chem. Eur. J. 2013, 19, 3315.
17. (a) Zhou, Y. J.; Zhang, Y.; Wang, J. B. Chin. J. Chem. 2017, 35, 621. (b) Chen, D.; Zhu, D. X.; Xu, M. H. J. Am. Chem. Soc. 2016, 138, 1498.
18. (a) Senanayake, C. H.; Krishnamurthy, D.; Gallou, I. In Handbook of Chiral Fine Chemicals; Ager, D., Ed.; Taylor&Francis Ed.: New York, 2005, 117. (b) Senanayake, C. H.; Krishnamurthy, D.; Gallou, I. In Handbook of Chiral Fine Chemicals; Ager, D., Ed.; Taylor & Francis Ed.: New York, 2005, 319. (c) Senanayake, C. H.; Krishnamurthy, D.; Gallou, I. In Handbook of Chiral Fine Chemicals; Ager, D., Ed.; Taylor&Francis Ed.: New York, 2005, 457.
19. (a) Lyle, T. A.; Wiscount, C. M.; Guare, J. P.; Thompson, W. J.; Anderson, P. S.; Darke, P. L.; Zugay, J. A.; Emini, E. A.; Schleif, W. A.; Quintero, J. C.; Dixon, R. A. F.; Sigal, I. S.; Huff, J. R. J. Med. Chem. 1991, 34, 1228. (b) Dorsey, B. D.; Levin, R. B.; McDaniel, S. L.; Vacca, J. P.; Guare, J. P.; Darke, P. L.; Zugay, J. A.; Emini, E. A.; Schleif, W. A.; Quintero, J. C.; Lin, J. H.; Chen, I.-W.; Holloway, M. K.; Fitzgerald, P. M. D.; Axel, M. G.; Ostovic, D.; Anderson, P. S.; Huff, J. R. J. Med. Chem. 1994, 37, 3443. (c) Reider, P. J. Chimia 1997, 51, 306.
20. (a) Alterman, M.; Björsne, M.; Mühlman, A.; Classon, B.; Kvarnström, I.; Danielson, H.; Markgren, P.-O.; Nillroth, U.; Unge, T.; Hallberg, A.; Samuelsson, B. J. Med. Chem. 1998, 41, 3782. (b) scarsson, K.; Classon, B.; Kvarnström, I.; Hallberg, A.; Samuelsson, B. Can. J. Chem. 2000, 78, 829. (c) Mühlman, A.; Classon, B.; Hallberg, A.; Samuelsson, B. J. Med. Chem. 2001, 44, 3402. (d) Mühlman, A.; indberg, J.; Classon, B.; Unge, T.; Hallberg, A.; Samuelsson, B. J. Med. Chem. 2001, 44, 3407.
21. (a) Chen, P. H..; Savage, N. A.; Dong, G. Tetrahedron Lett. 2014, 70, 4135 (b) Dhawan, K. L.; Gowland, B. D.; Durst, T. J. Org. Chem. 1980, 45, 922. (c) Neudeck H.; Brinker, U. H. Tetrahedron Lett. 2005, 46, 1893.
22. Gopula, B.; Lee, W.Z.; Wu, H. L. Chem. Asian J. 2013 , 8, 80.
23. (a) [8v, 8w, 8x, 8xa, 8y, 8ya are followed by this procedure] Hu, S.; Neckers, D. C. J. Org. Chem. 1996, 61, 6407. (b) [8z is followed by this procedure] Thai, K.; Langdon, S. M.; Bilodeau, F.; Gravel, M. Org. Lett. 2013, 15, 2214.
24. Diazo 38 are belongs to these procedures. (a) Song, B.; Wang, S.; Sun, C.; Deng, H. ; Xu, B. Tetrahedron Lett. 2007,48, 8982. (b) Marti, C.; Carreira, E. M. J. Am. Chem. Soc., 2005, 127, 11505. (c) Plabst, M.; Stock, N.; Bein, T. Crystal Growth & Design, 2009, 9, 5049.