本論文主要以過渡金屬催化為主軸，經由第一列過渡金屬: 鎳金屬、鐵金屬與π組件化合物及有機金屬試劑進行偶合反應，開發出新穎性合成方法。
第一章節主要著墨於鎳金屬催1,6-烯炔與1,7-烯炔分子與雙聯頻哪醇硼酸酯進行烯基硼酸酯環化反應形成高位向及立體選擇性之產物。該反應的高度化學選擇性取決於烯炔化合物的使用類型。所得到的硼酸酯化合物可以很成功的進行官能基的轉換。
第二章節續鎳金屬催化系統進行雙烯酮化合物與有機硼酸進行1,4-加成反應建立四級碳中心，且具有高度的區域選擇性。此催化反應是用於各種芳香基或苯乙烯基酸取代之雙烯酮化合物，且有機硼酸並不需要任何添加劑的的活化。
第三章節研究致力於鐵試劑與1,6-烯炔化合物進行鹵化–環化反應，這是一個簡單、有效和經濟的方法來合成苯並呋喃酮，此反應的優點，包括溫和的鹵化條件下，轉化率高，反應時間短和高的產率。
最後的章節，提供了一種經濟有效的途徑，利用鐵催化系統將炔類化合物及以二氧化碳作為碳原子的來源，此α,β-不飽和羧酸產物，可以很容易地轉化苯並呋喃-2-酮，這是存在於各種天然產物和生物活性分子的骨架。

This thesis describes development of new synthetic methods with π components and organometallic reagents using more abundant first-row transition metal catalyst such as, Nickel and Iron.
In first chaper, nickel-catalyzed borylative cyclization of 1,6- and 1,7-enynes with bis(pinacolato)diboron is described. The reaction is highly chemo- and stereoselective which majorly depends on the type of enyne employed. The utility of alkenylboronates in coupling reactions and functional group transformation reactions were demonstrated.
The 2nd chaper reveals nickel-catalyzed highly regioselective 1,4-addition reaction of organo boronic acids to dienones to form all-carbon quater-nary center. The catalytic reaction is compatible with a variety of aryl- and styrylboronic acids and dienones and does not require any additive for the activation of the boronic acids.
Chapter 3 depicts iron promoted halocyclizations of 1,6-enynes. we have developed a simple, efficient and economical method for the synthesis of benzofuranone. This method offers several advantages including mild halogenation condition, high conversion, short reaction time and good yields.
The final chapter deals about an economically efficient synthesis of vinyl carboxylic acids by iron-catalyzed hydrocarboxylation of internal alkynes using carbon dioxide as a carbon source. The α,β-unsaturated carboxylic acids could be easily transformed to corresponding benzofuran-2-one skeletons which are present in various natural product and bioactive molecules.

第一章
(1) (a) Aubert, C.; Buisine, O.; Malacria, M. Chem. Rev. 2002, 102, 813. (b) Jimenez-Nunez, E.; Echavarren, A. M. Chem. Rev. 2008, 106, 3326. (c) Michelet, V.; Toullec, P. Y.; Genet, J.-P. Angew. Chem., Int. Ed. 2008, 47, 4268. (d) Trost, B. M. Acc. Chem. Res. 1990, 23, 34. (e) Negishi, E.-I.; Coperet, C.; Ma, S.; Liou, S.-Y.; Liu, F. Chem. Rev. 1996, 96, 365. (f) Ojima, I.; Tzamarioudaki, M.; Li, Z.; Donovan, R. J. Chem. Rev. 1996, 96, 635.
(2) (a) Sato, Y.; Imakuni, N.; Mori, M. Adv. Synth. Catal. 2003, 345, 488. (b) Sato, Y.; Imakuni, N.; Hirose, T.; Wakamatsu, H.; Mori, M. J. Organomet. Chem. 2003, 687, 392. (c) Onozawa, S.-Y.; Hatanaka, Y.; Choi, N.; Tanaka, M. Organometallics 1997, 16, 8389. (d) Onozawa, S.-Y.; Hatanaka, Y.; Tanaka, M. Chem. Commun. 1997, 1229. (e) Hong, Y.-T.; Yoon, S.-K.; Kang, S.-K.; Yu, C.-M. Eur. J. Org. Chem. 2004, 4638.
(3) (a) Ojima, I.; Vu, A. T.; Lee, S.-Y; McCullagh, J. V.; Moralee, A. C.; Fujiwara, M.; Hoang, T. H. J. Am. Chem. Soc. 2002, 124, 9164. (b) Kisanga, P.; Widenhoefer, R. A. J. Am. Chem. Soc. 2000, 122, 10017. (c) Lautens, M.; Mancuso, J. Org. Lett. 2000, 2, 671. (d) Chakrapani, H.; Liu, C.; Widenhoefer, R. A. Org. Lett. 2003, 5, 157.
(4) (a) Mannathan, S.; Jeganmohan, M.; Cheng, C.-H. Angew. Chem., Int. Ed. 2009, 48, 2192. (b) Yang, C.-M.; Jeganmohan, M.; Parthasarathy, K.; Cheng, C.-H. Org. Lett. 2010, 12, 3610. (c) Chen, H.; Huang, Z.; Hu, X.; Tang, G.; Xu, P.; Zhao, Y.; Cheng, C.-H. J. Org. Chem. 2011, 76, 2338. (d) Yang, C.-M.; Mannathan, S.; Cheng, C.-H. Chem. Eur. J. 2013, 19, 12212.
(5) (a) Fagnou, K.; Lautens, M. Chem. Rev. 2003, 103, 169. (b) Miyaura, N.; Suzuki, A. Chem. Rev. 1995, 95, 2457. (c) Hayashi, T.; Yamasaki, K. Chem. Rev. 2003, 103, 2829. (d) Miura, T.; Murakami, M. Chem. Commun. 2007, 217. (e) Youn, S. W. Eur. J. Org. Chem. 2009, 16, 2597.
(6) Miura, T.; Takahashi, Y.; Murakami, M. Org. Lett. 2008, 10, 1743.
(7) Tobisu, M.; Fujihara, H.; Koh, K.; Chatani, N. J. Org. Chem. 2010, 75, 4841.
(8) Hong, S.; Liu, M.; Zhang, W.; Zeng, Q.; Deng, W. Tetrahedron Lett. 2015, 56, 2297.
(9) Marco-Martinez, J.; Lopez-Carrillo, V.; Bunuel, E.; Simancas, R.; Cardenas, D. J. Am. Chem. Soc. 2007, 129, 1874.
(10) Marco-Martinez, J.; Bunuel, E.; Munoz-Rodriguez, R.; Cardenas, D. J. Org. Lett. 2008, 10, 3619.
(11) Camelio, A. M.; Barton, T.; Guo, F.; Shaw, T.; Siegel, D. Org. Lett. 2011, 13, 1517.
(12) Pardo-Rodriguez, V.; Bunuel, E.; Collado-Sanz, D.; Cardenas, D. J. Chem. Commun. 2012, 48, 10517.
(13) Lopez-Duran, R.; Martos-Redruejo, A.; Bunuel, E.; Pardo-Rodriguez, V.; Cardenas, D. J. Chem. Commun. 2013, 49, 10691.
(14) Martos-Redruejo, A.; Lopez-Duran, R.; Bunuel, E.; Cardenas, D. J. Chem. Commun. 2014, 50, 10094.
(15) Persson, A. K. A.; Jiang, T. ; Johnson, M. T.; Backvall, J.-E. Angew. Chem., Int. Ed. 2011, 50, 6155.
(16) Deng, Y.; Bartholomeyzik, T.; Backvall, J.-E. Angew. Chem., Int. Ed. 2013, 52, 6283.
(17) Jiang. T.; Bartholomeyzik, T.; Mazuela, J.; Willersinn, J.; Backvall, J.-E. Angew. Chem., Int. Ed. 2015, 54, 6024.
(18) Kamijo, S.; Dudley, G. B. J. Am. Chem. Soc. 2006, 128, 6499.
(19) Kai, K.; Tani, A.; Hayashi, H. Bioorg. Med. Chem. 2010, 18, 3776.
第二章
(1) Ranny, M.; office, U. s. p., Ed. 1925; Vol. 733952, p 2.
(2) Yang, T.-K.; Lee, D.-S.; Haas, J. In Encyclopedia of Reagents for Organic Synthesis; John Wiley & Sons, Ltd; 2001.
(3) (a) Rossiter, B. E.; Swingle, N. M. Chem. Rev. 1992, 92, 771. (b) Perlmutter, P. Conjugate Addition Reactions in Organic Synthesis; 1 ed.; Pergamon, 1992.
(4) Shirakawa, E.; Yasuhara, Y.; Hayashi, T. Chem. Lett. 2006, 35, 768.
(5) Hirano, K.; Yorimitsu, H.; Oshima, K. Org. Lett. 2007, 9, 1541.
(6) Meng, J.-J.; Gao, M.; Dong, M.; Wei, Y.-P.; Zhang, W.-Q. Tetrahedron Lett. 2014, 55, 2107.
(7) Chen, W.; Sun, L.; Huang, X.; Wang, J.; Peng, Y.; Song, G. Adv. Synth. Catal. 2015, 357, 1474.
(8) Hawner, C.; Alexakis, A. Chem. Commun. 2010, 46, 7295.
(9) (a) Feringa, B. L. Acc. Chem. Res. 2000, 33, 346. (b) Hird, A. W.; Hoveyda, A. H. J. Am. Chem. Soc. 2005, 127, 14988.
(10) (a) d’Augustin, M.; Palais, L.; Alexakis, A. Angew. Chem., Int. Ed. 2005, 44, 1376. (b) May, T. L.; Brown, M. K.; Hoveyda, A. H. Angew. Chem., Int. Ed. 2008, 47, 7358. (c) Hawner, C.; Li, K.; Cirriez, V.; Alexakis, A. Angew. Chem., Int. Ed. 2008, 47, 8211. (d) Vuagnoux- d’Augustin, M.; Alexakis, A. Chemistry 2007, 13, 9647.
(11) (a) Henon, H.; Mauduit, M.; Alexakis, A. Angew. Chem., Int. Ed. 2008, 47, 9122. (b) Kehrli, S.; Martin, D.; Rix, D.; Mauduit, M.; Alexakis, A. Chemistry 2010, 16, 9890. (c) Martin, D.; Kehrli, S.; d’Augustin, M.; Clavier, H.; Mauduit, M.; Alexakis, A. J. Am. Chem. Soc. 2006, 128, 8416. (d) Matsumoto, Y.; Yamada, K.-I.; Tomioka, K. J. Org. Chem. 2008, 73, 4578.
(12) Alexakis, A.; Benhaim, C.; Rosset, S.; Humam, M. J. Am. Chem. Soc. 2002, 124, 5262.
(13) d’Augustin, M.; Palais, L.; Alexakis, A. Angew. Chem., Int. Ed. 2005, 44, 1376.
(14) Shintani, R.; Takeda, M.; Nishimura, T.; Hayashi, T. Angew. Chem., Int. Ed. 2010, 49, 3969.
(15) Lin, S.; Lu, X. Org. Lett. 2010, 12, 2536.
(16) Kikushima, K.; Holder, J. C.; Gatti, M.; Stoltz, B. M. J. Am. Chem. Soc. 2011, 133, 6902.
(17) (a) Alexakis, A.; Winn, C. L.; Guillen, F.; Pytkowicz, J.; Roland, S.; Mangeney, P. Adv. Synth. Catal. 2003, 345, 345. (b) Tissot, M.; Poggiali, D.; Henon, H.; Muller, D.; Guenee, L.; Mauduit, M.; Alexakis, A. Chemistry 2012, 18, 8731.
(18) (a) Togashi, M.; Ozawa, S.; Abe, S.; Nishimura, T.; Tsuruga, M.; Ando, K.; Tamura, G.; Kuwahara, S.; Ubukata, M.; Magae, J. J. Med. Chem. 2003, 46, 4113. (b) Ji-Hak, J.; Yun-Jeong, J.; Hyun-Ji, C.; Jae-Moon, S.; Jeong-Han, K.; Kwan-Kyu, P.; Yoon-Yub, P.; Il-Kyung, C.; Hyeun-Wook, C.; Junji, M.; Shin-Sung, K.; Young-Chae, C. J. Cell. Biochem. 2012, 113, 1302.
(19) Singh, S. B.; Zink, D. L.; Bill, G. F.; Jenkins, R. G.; Silverman, K. C.; Lingham, R. B. Tetrahedron Lett. 1995, 36, 4935.
(20) Li, X. L.; Zhao, B. X.; Huang, X. J.; Zhang, D. M.; Jiang, R. W.; Li, Y. J.; Jian, Y. Q.; Wang, Y.; Li, Y. L.; Ye, W. C. Org. Lett. 2014, 16, 224.
(21) McCrae, D. A.; Dolby, L. J. Org. Chem. 1977, 42, 1607.
(22) (a) Rogers, R. L.; Moore, J. L.; Rovis, T. Angew. Chem., Int. Ed. 2007, 46, 9301. (b) Canovese, L.; Visentin, F.; Levi, C.; Santo, C. J. Organomet. Chem. 2008, 693, 3324. (c) Defieber, C.; Grutzmacher, H.; Carreira, E. M. Angew. Chem., Int. Ed. 2008, 47, 4482. (d) Johnson, J. B.; Rovis, T. Angew. Chem., Int. Ed. 2008, 47, 840. (e) Herndon, J. W. Coord. Chem. Rev. 2009, 253, 1517. (f) Gandeepan, P.; Cheng, C.-H. J. Am. Chem. Soc. 2012, 134, 5738. (g) Gandeepan, P.; Cheng, C.-H. Org. Lett. 2013, 15, 2084. (h) Chen, Q.; Chen, C.; Guo, F.; Xia, W. Chem. Commun. 2013, 49, 6433. (i) Kantchev, E. A. B. Chem. Sci. 2013, 4, 1864.
第三章
(1) Liu, H.; Chen, C.; Wang, L.; Tong, X. Org. Lett. 2011, 13, 5072.
(2) a) Xu, T.; Yu, Z.; Wang, L. Org. Lett. 2009, 11, 2113; b) Mukaiyama, T.; Murakami, M. Synthesis 1987, 12, 1043; c) Trost, B. M.; Chen, D. W. C. J. Am. Chem. Soc. 1996, 118, 12541; d) Sammakia, T.; Smith, R. S. J. Am. Chem. Soc. 1994, 116, 7915; e) Denmark, S. E.; Almstead, N. G. J. Am. Chem. Soc. 1991, 113, 8089; f) Kang, S.-K.; Kim, Y.-M.; Ha, Y.-H.; Yu, C.-M.; Yang, H.; Lim, Y. Tetrahedron Lett. 2002, 43, 9105.
(3) Li, H.; Loh, T.-P. J. Am. Chem. Soc. 2008, 130, 7194.
(4) Yamazaki, S.; Takebayashi, M. The J. Org. Chem. 2011, 76, 6432.
(5) Taniguchi, T.; Fujii, T.; Ishibashi, H. The J. Org. Chem. 2010, 75, 8126.
(6) Fukushima, Y.; Yamazaki, S.; Ogawa, A. Org. Biomol. Chem. 2014, 12, 3964.
(7) Yeh, M.-C. P.; Fang, C.-W.; Lin, H.-H. Org. Lett. 2012, 14, 1830.
(8) Dal Zotto, C.; Wehbe, J.; Virieux, D.; Campagne, J.-M. Synlett 2008, 13, 2033.
(9) Sawama, Y.; Goto, R.; Nagata, S.; Shishido, Y.; Monguchi, Y.; Sajiki, H. Chem. Eur. J. 2014, 20, 2631.
(10) Gharpure, S. J.; Shelke, Y. G.; Kumar, D. P. Org. Lett. 2015, 17, 1926.
(11) Strom, K. R.; Impastato, A. C.; Moy, K. J.; Landreth, A. J.; Snyder, J. K. Org. Lett. 2015, 17, 2126.
(12) He, Z.-T.; Tian, B.; Fukui, Y.; Tong, X.; Tian, P.; Lin, G.-Q. Angew. Chem., Int. Ed. 2013, 52, 5314.
(13) Liu, P.; Fukui, Y.; Tian, P.; He, Z.-T.; Sun, C.-Y.; Wu, N.-Y.; Lin, G.-Q. J. Am. Chem. Soc. 2013, 135, 11700.
(14) Takenaka, K.; Mohanta, S. C.; Sasai, H. Angew. Chem., Int. Ed. 2014, 53, 4675.
第四章
(1) Yeung, C.; Dong, V. Top. Catal. 2014, 57, 1342.
(2) Ukai, K.; Aoki, M.; Takaya, J.; Iwasawa, N. J. Am. Chem. Soc. 2006, 128, 8706.
(3) a) Ohishi, T.; Nishiura, M.; Hou, Z. Angew. Chem., Int. Ed. 2008, 47, 5792; b) Takaya, J.; Tadami, S.; Ukai, K.; Iwasawa, N. Org. Lett. 2008, 10, 2697.
(4) Zhang, X.; Zhang, W.-Z.; Shi, L.-L.; Guo, C.-X.; Zhang, L.-L.; Lu, X.-B. Chem. Commun. 2012, 48, 6292.
(5) Ochiai, H.; Jang, M.; Hirano, K.; Yorimitsu, H.; Oshima, K. Org. Lett. 2008, 10, 2681.
(6) Gooßen, L. J.; Rodríguez, N.; Manjolinho, F.; Lange, P. P. Adv. Synth. Catal. 2010, 352, 2913.
(7) Dingyi, Y.; Yugen, Z. Green Chem. 2011, 13, 1275.
(8) Zhang, L.; Cheng, J.; Ohishi, T.; Hou, Z. Angew. Chem., Int. Ed. 2010, 49, 8670.
(9) Mizuno, H.; Takaya, J.; Iwasawa, N. J. Am. Chem. Soc. 2011, 133, 1251.
(10) Fujihara, T.; Nogi, K.; Xu, T.; Terao, J.; Tsuji, Y. J. Am. Chem. Soc. 2012, 134, 9106.
(11) Sasaki, Y.; Inoue, Y.; Hashimoto, H. J. Chem. Soc., Chem. Commun. 1976, 15, 605.
(12) Louie, J.; Gibby, J. E.; Farnworth, M. V.; Tekavec, T. N. J. Am. Chem. Soc. 2002, 124, 15188.
(13) Greenhalgh, M. D.; Thomas, S. P. J. Am. Chem. Soc. 2012, 134, 11900.
(14) Ilies, L.; Yoshida, T.; Nakamura, E. J. Am. Chem. Soc. 2012, 134, 16951.
(15) Fujihara, T.; Xu, T.; Semba, K.; Terao, J.; Tsuji, Y. Angew. Chem., Int. Ed. 2011, 50, 523.
(16) Li, S.; Yuan, W.; Ma, S. Angew. Chem., Int. Ed. 2011, 50, 2578.
(17) Alami, M.; Liron, F.; Gervais, M.; Peyrat, J.-F.; Brion, J.-D. Angew. Chem., Int. Ed. 2002, 41, 1578.
(18) Fager-Jokela, E.; Muuronen, M.; Khaizourane, H.; Vázquez-Romero, A.; Verdaguer, X.; Riera, A.; Helaja, J. J. Org. Chem. 2014, 79, 10999.
(19) a) Tricotet, T.; Fleming, P.; Cotter, J.; Hogan, A.-M. L.; Strohmann, C.; Gessner, V. H.; O’Shea, D. F. J. Am. Chem. Soc. 2009, 131, 3142; b) Cheng, X.-F.; Li, Y.; Su, Y.-M.; Yin, F.; Wang, J.-Y.; Sheng, J.; Vora, H. U.; Wang, X.-S.; Yu, J.-Q. J. Am. Chem. Soc. 2013, 135, 1236; c) Marelli, C.; Monti, C.; Galli, S.; Masciocchi, N.; Piarulli, U. Tetrahedron 2006, 62, 8943.