本論文研究的主題是利用金金屬催化劑催化在胺類帶有強推電子基的苯環合成出的炔醯胺與烯醇醚及腈類反應，進行分子間[4+2]環加成反應，分別得到四氫喹啉和喹唑啉的核心結構，兩者皆為天然物及藥物上常見的主架構。這種新的環加成反應的效用適用在廣泛範圍的炔醯胺和烯醇醚及腈類，具有良好的官能基容忍度。

The thesis describes the gold-catalyzed intermolecular [4+2] cycloadditions of ynamides with vinyl ethers and nitriles for synthesis tetrahydroquinoline and quinazoline. The feature of our thesis is the ynamide is coupling by the amine with the aryl group which contains the strong donating group. Both of tetrahydroquinoline and quinazoline are common main structure of medicines and natural products. The utility of this new cycloaddition is applicable by wide range of ynamides and nitriles.

謝誌....................................................I
中文摘要................................................II
英文摘要...............................................III
目錄...................................................IV
表目錄.................................................VI
圖目錄................................................VII
附件目錄...............................................IX
英文縮寫對照表........................................XIII
第一節 緒論..............................................1
第二節 文獻回顧...........................................2
2-1藉由過渡金屬催化進行分子間環化反應..................... 2
2-2藉由金金屬催化1,3-雙烯-5-炔及腈類進行[4+2]環化反應..... 3
2-3藉由金金屬催化烯類及炔類進行分子間[2+2]環化反應......... 4
2-4金催化炔醯胺與烯烴進行分子間[4+2]和[2+2+2]環化反應..... 5
2-5藉由金催化炔醯胺與亞胺進行分子間[4+2]環化反應........... 7
2-6金催化炔醯胺與腈類進行分子間[2+2+2]環化反應............ 8
2-7金催化丙酸叔丁酯與腈類進行分子間[4+2]環化反應.......... 9
2-8金催化炔醯胺與腈類進行分子間[2+2+2]環化反應........... 10
第三節 結果與討論.........................................11
3-1 實驗動機與構思...................................... 11
3-2 炔醯胺及烯醇醚的最佳化反應條件........................ 12
3-3 金催化多種炔醯胺與烯醇醚進行[4+2]-環加成反應的範圍..... 14
3-4 炔醯胺及腈類的最佳化反應條件.......................... 17
3-5 金催化多種炔醯胺與腈類進行[4+2]-環加成反應的範圍........19
3-6反應機構探討......................................... 24
3-7 炔醯胺與烯醇醚反應產物之對映體過量百分數(ee值)探討..... 26
3-8 喹唑啉產物之應用.................................... 29
3-9 結構鑑定........................................... 30
第四節 結論..............................................31
第五節 實驗部分..........................................32
5-1 實驗的一般操作...................................... 32
5-2 實驗基質之合成...................................... 34
1. 基質1a之合成方法..................................... 34
2. 基質1b之合成方法..................................... 36
3. 基質1o之合成方法..................................... 38
4. 基質1t之合成方法..................................... 40
5. 基質4c之合成方法..................................... 41
6. 基質4k之合成方法..................................... 42
7.化合物5va’之合成方法.................................. 43
5-3 催化反應之操作...................................... 44
1.3aa合成實驗操作步驟................................... 44
2.5ha合成實驗操作步驟................................... 45
5-4 實驗光譜數據資料.................................... 46
5-5 化合物3fb的X-射線結晶結構和數據...................... 88
第六節 參考文獻..........................................97

[1] O. Diels, K. Alder, Liebigs Ann. Chem. 1928, 460, 98-122.
[2] (a) J. A. Berson, Tetrahedron 1992, 48, 3-17. (b) K. C. Nicolaou; Scott A. Snyder; T. Montagnon; G. Vassilikogiannakis, Angew. Chem. Int. Ed. 2002, 41, 1668-1698 (c) C. C. Nawrat; C. J. Moody, Angew. Chem. Int. Ed. 2014, 53, 2056-2077 (d) V. Eschenbrenner-Lux; K. Kumar; H. Waldmann; Angew. Chem. Int. Ed. 2014, 53, 11146-11157 (e) J. W. Ren; J. Wang; J. A. Xiao; J. Li; H. Y. Xiang; X. Q. Chen; H. Yang, J. Org. Chem. 2017, 82, 6441-6449
[3] for Ru- (a) Yamamoto, Y.; Ogawa, R.; Itoh, K. J. Am. Chem. Soc. 2001, 123, 6189. (b) Y. Zhao; Z. He; S. Li; J. Tang; G. Gao; J. Lan; J. You, Chem. Commun.2016, 52, 3187-3190 (c) T. Watanabe; Y. Mutoh; S. Saito, J. Am. Chem. Soc. 2017, 139, 7749-7752
[4] for Ir- Onodera, G.; Shimizu, Y.; Kimura, J.-N.; Kobayashi, J. Ebihara, Y.; Kondo, K.; Sakata,K.; Takeuchi, R. J. Am. Chem. Soc. 2012, 134, 10515.
[5] for Co- (a) A. Goswami; T. Ito; S. Okamoto; Adv. Synth. Catal. 2007, 349, 2368-2374 (b) K. Komeyama; Y. Okamoto; K. Takaki, Angew. Chem. Int. Ed. 2014, 53, 11325-11328 (c) S. Yu; C. Wu; S. Ge, J. Am. Chem. Soc. 2017, 139, 6526-6529
[6] (a) M. E. Muratore; A. Homs; C. Obradors; A. M. Echavarren, Chem. Asian J. 2014, 9, 3066 (b) P. R. Chopadea; J. Louie, Adv. Synth. Catal. 2006, 348, 2307-2327 (c) G. Masson; C. Lalli; M. Benohoud; G. Dagousset, Chem. Soc. Rev. 2013, 42, 902-923 (d) M. R. Shaaban; R. El-Sayed; A. H. M. Elwahy, Tetrahedron, 2011, 67, 6095
[7] Jose´ Barluenga; Manuel Angel Ferna´ndez-Rodrı´guez; Patricia Garcı´a-Garcı´a; and Enrique Aguilar, J. Am. Chem. Soc. 2008, 130, 2764-2765
[8] Vero´nica Lo´ pez-Carrillo; A. M. Echavarren, J. Am. Chem. 　　 Soc. 2010, 132, 9292-9294
[9] C. Obradors; D. Leboeuf; J. Aydin; A. M. Echavarren, Org. Lett., Vol. 15, No. 7, 2013, 1576-1579
[10] R. B. Dateer; B. S. Shaibu; R. S. Liu, Angew. Chem. Int. Ed. 2012, 51, 113-117
[11] Z. Xin; S. Kramer; J. Overgaard; T. Skrydstrup, Chem Eur. J. 2014, 20, 7926-7930
[12] S. N. Karad; R. S. Liu, Angew. Chem. Int. Ed. 2014, 53, 9072-9076
[13] S. N. Karad; W. K.Chung; R. S. Liu, Chem. Sci., 2015, 6, 5964–
5968
[14] Y. L. Chen; P. Sharma; R. S. Liu, Chem. Commun., 2016, 52,
3187-3190
[15] T. Itoh; M. Yokoya; K. Miyauchi; K. Nagata; A. Ohsawa, Org. Lett., Vol. 5, No. 23, 2003, 4301-4304
[16] (a) Antonello A; Hrelia P, Leonardi A, et al. J Med Chem. 2005;48:28; (b) Rosini M; Antonello A; Cavalli A, et al. J Med Chem. 2003;46:4895.
[17] Gundla R; Kazemi R; Sanam R, et al. J Med Chem. 2008;51:3367
[18] (a) Rewcastle GW; Palmer BD; Bridges AJ, et al. J Med Chem. 1996;39:918; (b) Luth A; Lowe W, Eur J Med Chem. 2008;43:1478.