本論文描述了利用金或銅金屬鹽類的合成有機轉換新途徑。使用這些金屬能夠將易取得的合成基質，經由溫和、高選擇性、高效氧化的轉換途徑得到具有廣泛合成用途的含氮、氧以及硫的複雜有機分子。為了更清楚地瞭解本文，本文分成四個章節。第一章聚焦於金催化氧化環化4-丙二烯-1-炔與8-甲基喹啉氧化物。根據不同的丙二烯基取代物，此催化反應產生多樣含氮及氧的異環之理想產物。此反應包含由丙二烯攻擊初步形成的α-氧-金卡賓，產生烯丙基陽離子中間體，再進行消除或親核加成反應形成多樣的環化產物。而本處所獲得的中間體α-氧-金卡賓之結果，表現出碳陽離子的性質。
第二章論述了銅催化含氧氧化N-羥基丙炔胺結構重排的曼尼反應。透過含氧氧化這些易取得的3-N-羥基氨基親-1-炔與水、醇或硫醇，可以得到不同的3-取代的3-氨基-2-烯-1-酮。利用克萊森重排以及金催化環化反應，我們開發一連串烯丙基醇、炔醇和烯醇的連續反應，來合成出更具分子複雜性的新產物。
第三章描述了以銅催化及過氧化叔丁醇氧化N, N-二烷基苯胺、飽和氧或硫雜環
之波瓦羅夫反應來形成四氫異喹啉衍生物。使用廉價的烷烴類物質作為四和兩個原子建構單元有利機構和經濟效益，這項工程也代表首次成功催化[4+ 2]環加成反應，且不使用 [4p]或[2p]為最初基序。
第四章呈現了金催化N-羥基苯胺和丙二烯合成2,3-二取代吲哚衍生物；透過甲醛作為添加劑產生原位之硝酮。於合理的範圍內，這種合成方法通用丙二烯和N-羥基苯胺，從而進一步凸顯其綜合效用。

This dissertation describes development of new synthetic organic transformations by using gold or copper metal salts. The use of these metals enables mild, selective and efficient oxidative transformations of readily available substrates to wide range of synthetically useful nitrogen, oxygen and sulfur containing complex organic molecules. For better understanding the thesis is divided into four chapters.
The first chapter deals with the Gold-catalyzed oxidative cyclization of 4-allenyl-1-ynes with 8-methylquinoline oxide. The catalytic reaction produces diverse products bearing N and O heterocycles depending on the allenyl substituents. This reaction comprises initial formation of α-oxo gold carbenes that are attacked by allene to form allyl cation intermediates which either undergoes elimination or nucleophilic addition to afford diverse cyclic products. The results obtained here manifested that the intermediate α-oxo-gold carbenes has carbocation character.

The second chapter deals with the Cu-catalyzed aerobic oxidative Mannich reactions with a skeletal rearrangement of N-hydroxyl propargylamines. These aerobic oxidations of readily available 3-N-hydroxyaminopro-1-ynes with water, alcohols, or thiols afford diverse 3-substituted 3-amino-2-en-1-ones. We developed cascade or sequential reactions of allylic alcohols, alkynols, and allenols, to involve a Claisen rearrangement or gold catalyzed cyclizations, providing new products with molecular complexity.

The third chapter describes the Cu-catalyzed oxidative Povarov reactions between N,N-dialkylanilines and saturated oxa- or thiacycles with tert-butyl hydroperoxide (TBHP) to form tetrahydroisoquinoline derivatives. The use of cheap alkane based substances as four- and two-atom building units is of mechanistic and practical interest, this work also represents the first achievement of catalytic [4+2]-cycloaddition using neither [4p]- nor [2p]-motifs initially.

The fourth chapter presents gold-catalyzed syntheses of 2,3-disubstituted indole derivatives from N-hydroxyanilines and allenes; with benzaldehyde as an additive to generate nitrones in situ. This synthetic method is compatible with reasonable range of allenes and N-hydroxyanilines, thus further highlighting its synthetic utility.

Chapter I
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Chapter II
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[32] CCDC:- 998937 (2-3g) and 998936 (2-3l) contain the supplementary crystallographic data for this paper.
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Chapter III
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[27] The reactions of N,N-dimethylaniline and THF with Pd(OAc)2 (0.5 equiv.) in the absence of oxidants were reported to give distinct products in low yields for most aniline substrates; see ref. 27a. (a) Sakakibara, T.; Karasumara, S.; Kawano, I.; J. Am. Chem. Soc. 1985, 107, 6417. (b) Zhang, J.; Li, C.-J. J. Org. Chem. 2002, 67, 3969. (c) Lang, Y.; Souza, F. E. S.; Xu, X.; Taylor, N. J.; Assoud, A.; Rodrigo, R. J. Org. Chem. 2009, 74, 5429. (d) Zhao, Y.; Ang, L. A.; Ng, A. W. T.; Yeung, Y.-Y. RSC Adv. 2013, 3, 19765.
[28] We have conducted a control experiment to confirm that the reaction of Cu(s) with TBHP (2 equiv.) in water (90 1C, 24 h) gave water soluble Cu-complexes in 5% yield. This salt contained Cu in 28 wt% and its 5 mol % Cu loading enabled a cycloaddition of aniline III-2b (1.0 equiv.) with THF (10 equiv.) in water to yield desired III-3b in 75% yield.
[29] CCDC 1039307 (III-3f).
[30] Thermal decomposition of TBHP without metal catalyst can proceed at 120 oC whereas the temperature was 90 oC for eqn (1). See: He, T.; Zhang, L.; Wang, L.; Wang, M. Org. Lett. 2011, 13, 5016.
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Chapter IV
[1] (a) Sundberg, R. J. The Chemistry of Indoles; Academic Press: New York, 1970. (b) Sundberg, R. J. Pyrroles and Their Benzoderivatives: Synthesis and Applications. In Comprehensive Heterocyclic Chemistry; Katritzky, A. R., Rees, C. W., Eds.; Pergamon: Oxford, U.K., 1984; Vol. 4, pp 313. (c) Sundberg, R. J. In Best Synthetic Methods, Indoles; Academic Press: New York, 1996; pp 7. (d) Joule, J. A. Indole and its Derivatives. In Science of Synthesis: Houben-Weyl Methods of Molecular Transformations; Thomas, E. J., Ed.; George Thieme Verlag: Stuttgart, Germany, 2000; Category 2, Vol. 10, Chapter 10.13. (e) Brown, R. K. In Indoles; Houlihan, W. J., Ed.; Wiley-Interscience: New York, 1972. (f) Sundberg, R. J. In Comprehensive Heterocyclic Chemistry II; Katritzky, A. R., Ress, C. W., Scriven, E. F. V., Bird, C. W., Eds.; Pergamon Press: Oxford, 1996; Vol. 2, p 119. (g) Gribble, G. W. Comprehensive Heterocyclic Chemistry II; Katritzky, A. R., Ress, C. W., Scriven, E. F. V., Bird, C. W., Eds.; Pergamon Press: Oxford, 1996; Vol. 2, p 207.
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