簡介
本論文介紹使用金鹽類進行有機轉化合成反應的新發展。我們使用這種軟性的alkynophilic金屬進行各種溫和條件反應和具有立體選擇性以及高效率的分子轉化反應而成功合成出高度官能基化的有機分子。為了更好地理解本論文，共分為四個章節加以討論。

第一章論述了1,2-氧芳基化反應，使用金催化腈與吡啶衍生氧化物。這是文獻上首次成功進行金催化氧芳基化反應，使用金的亞甲基作為反應啟動關鍵而產生benzo[d]azepine架構。例如氮雜環核心是自然界中最常見的架構以及廣泛普應用中的結構。這些反應也可合適地用於在分子間的三部分氧化劑，包括多樣alkenyldiazo酯類，腈，吡啶基氧化物來進行反應。

第二章討論金催化立體位向選擇可控制的[2+2+2]環加成ynamides分子的構築，其為藥學上重要的基本結構。這個新的環加成反應，具有的有優秀的位向選擇性並應用於廣泛的ynamides和腈分子。

第三章介紹了立體化學位向保留中效果優良的金催化[4+3]環加成環氧化物與 arenyanamides的反應。這種新的[4+3]環加成反應數據由大量的arenynamides分子和環氧化物產生。我們預測SN2型前側攻擊在環氧乙烷環的苯基上是導致立體化學保留的原因。

第四章介紹了金催化的1,2–difunctionalizations反應，aminoalkynes分子與包含氮和氧的氧化劑反應。在與IPrAuNTf2反應的條件下，nitrosobenzenes實現了一種新穎的反應，產生2 - oxoiminylamides然後進行硼氫化鈉還原得到2-氨基醇。

Abstract
This dissertation describes development of new synthetic organic transformations by using gold salts. The use of this soft alkynophilic metal enables mild, diastereoselective and efficient transformations of a variety of readily available substrates to wide range of synthetically useful highly functionalized products. For better understanding the thesis is divided into four chapters.
The first chapter deals with the gold-catalyzed 1,2-oxoarylations of nitriles with pyridine-derived oxides. This is the first success in the gold-catalyzed oxoarylations of nitriles using gold carbenes as initiators leading to benzo[d]azepine frameworks. Such azacyclic core is one of the most commonly encountering skeletons in nature and the core scaffold has a wide spread application in structural, biological importance. These oxoarylations were also achieved satisfactorily in intermolecular three-component oxidations, including diverse alkenyldiazo esters, nitriles, and pyridine-based oxides.

The second chapter deals with the gold-catalyzed regiocontrolled [2+2+2]-cycloadditions of ynamides with two discrete nitriles to construct 4-aminopyrimidine cores pharmaceutically important structural motifs. The utility of this new cycloaddition is manifested by the excellent regioselectivity with applicable ynamides and nitriles over a wide scope.

The third chapter describes the retention of stereochemistry in gold-catalyzed formal [4+3]-cycloaddition of epoxides with arenyanamides. The utility of this new [4+3]-Cycloaddition reaction is manifested by a wide scope of arenynamides and epoxides. An SN2-type front-side attack of phenyl at the oxiranyl ring is expected to cause the retention of stereochemistry.

The fourth chapter presents gold-catalyzed 1,2-difunctionalizations of aminoalkynes using Only N- and O-containing oxidants. In the presence of IPrAuNTf2, nitrosobenzenes implements a novel oxoimination of aminoalkynes to form 2-oxoiminylamides that are then subjected to NaBH4 reduction in situ to deliver 2-aminoalcohols.

Chapter1
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Chapter2
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[22] Karad, S. N.; Bhunia, S.; Liu, R.-S. Angew. Chem. 2012, 124, 8852; Angew. Chem. Int. Ed. 2012, 51, 8722.
[23] Reviews for ynamides, see ref. 13 and a) Wang, X.-N.; Yeom, H.-S.; Fang, L.-C.; He, S.; Ma, Z.-X.; Kedrowski, B. L.; Hsung, R. P. Acc. Chem. Res. 2014, 47, 560. b) DeKorver, K. A.; Li, H.; Lohse, A. G.; Hayashi, R.; Lu, Z.; Zhang, Y.; Hsung, R. P. Chem. Rev. 2010, 110, 5064.
[24] For Au-catalyzed reactions on ynamides, see ref. 14, 15 and selected examples: a) Vasu, D.; Hung, H. H.; Bhunia, S.; Gawade, S. A.; Das, A.; Liu, R.-S. Angew. Chem. 2011, 123, 7043; Angew. Chem. Int. Ed. 2011, 50, 6911. d) Rettenmeier, E.; Schuster, A. M.; Rudolph, M.; Rominger, F.; Gade, C. A.; Hashmi, A. S. K. Angew. Chem. 2013, 125, 5993; Angew. Chem. Int. Ed. 2013, 52, 5880. e) Kramer, S.; Odabachian, Y.; Overgaard, J.; Rottländer, M.; Gagosz, F.; Skrydstrup, T. Angew. Chem. 2011, 123, 5196; Angew. Chem. Int. Ed. 2011, 50, 5090. f) Davies, P. W.; Cremonesi, A.; Dumitrescu, L. Angew. Chem. 2011, 123, 9093; Angew. Chem. Int. Ed. 2011, 50, 8931.
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[26] Crystallographic data of compounds 2-1a (CCDC 1001397) and 2-2i (CCDC 1001398) were deposited at Cambridge Crystallographic Data Center.
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[28] We have examined the 13C NMR study for an equimolar mixture of benzonitrile and PPh3AuCl/AgSbF6 in CD2Cl2; the 13C signal of the nitrile appeared at 119.2 ppm, very close of that of free nitrile (118.8 ppm). This observation revealed that this gold catalyst had certain affinity toward nitrile.
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[31] Selected examples: a) Barluenga, J.; Fernández-Rodríguez, M. Á.; García-García, P.; Aguilar, E. J. Am. Chem. Soc. 2008, 130, 2764. b) Faustino, H.; López, F.; Castedo, L.; Mascareñas, J. L. Chem. Sci. 2011, 2, 633. c) Faustino, H.; Alonso, I.; Mascareñas, J. L.; López, F. Angew. Chem. 2013, 125, 6654; Angew. Chem. Int. Ed. 2013, 52, 6526.
[32] For synthesis of ynamides: see the published procedures: a) Mukherjee, A.; Dateer, R. B.; Chaudhuri, R.; Bhunia, S.; Karad, S. N.; Liu, R. S. J. Am. Chem. Soc. 2011, 133, 15372. b) Dateer, R. B.; Shaibu, B. S.; Liu, R.-S. Angew. Chem. 2012, 124, 117 – 121; Angew. Chem. Int. Ed. 2012, 51, 113. c) Karad, S. N.; Bhunia, S.; Liu, R.-S. Angew. Chem. 2012, 124, 8852; Angew. Chem. Int. Ed. 2012, 51, 8722. d) Zhang, Y.; Hsung, R. P.; Tracey, M. R.; Kurtz, K. C. M.; Vera, E. L. Org. Lett. 2004, 6, 1151. e) Gawade, S. A.; Huple, D. B.; Liu, R.-S. J. Am. Chem. Soc. 2014, 136, 2978. f) J. Lee, Y.-L. Zhong, R. A. Reamer, D. Askin, Org. Lett., 2003, 5, 4175. g) D. Vasu, H.-H. Hung, S. Bhunia, S. A. Gawade, A. Das, R.-S. Liu, Angew. Chem. 2011, 123, 7043–7046; Angew. Chem. Int. Ed. 2011, 50, 6911 – 6914.
[33] For transformation of a sulfonamide (3-4s) into an amine (3-4s’), see the published procedure: V. Coeffard, C. Thobie-Gautier, I. Beaudet, E. L. Grognec, J. P. Quintard, Eur. J. Org. Chem. 2008, 383 – 391.

Chapter3
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[11] Shim, J.-G.; Yamamoto, Y. J. Org. Chem. 1998, 63, 3067.
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[14] Evano, G.; Coste, A.; Jouvin, K. Angew. Chem. 2010, 122, 2902; Angew. Chem., Int. Ed. 2010, 49, 2840.
[15] Dateer, R. B.; Shaibu, B. S.; Liu, R.-S. Angew. Chem. 2012, 124, 117; Angew. Chem. Int. Ed. 2012, 51, 113.
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[18] For metal-catalyzed cycloaddition reactions, see selected reviews: a) Wender, P. A.; Verma, V. A.; Paxton, T. H. Acc. Chem. Res. 2008, 41, 40. b) Inglesby, P. A.; Evans, P. A. Chem. Soc. Rev. 2010, 39, 2791. c) Sohel, S. M. A.; Liu, R.-S. Chem. Soc. Rev. 2009, 38, 2269.
[19] For selected reviews for epoxides and aziridines, see: a) A. K. Yudin in Aziridines and Epoxides in Organic Synthesis, Wiley- VCH, Weinheim, 2006; b) Gothelf, K. V.; Jørgensen, K. A.
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[20] see ref. 9 and a) Madhushaw, R. J.; Li, C.-L.; Hu, J.-C.; Liu, R.-S. J. Am. Chem. Soc. 2001, 123, 7427. b) Shen, K.-H.; Lush, S.-F.; Chen, T.-L.; Liu, R.-S. J. Org. Chem. 2001, 66, 8106. [21] For gold-catalyzed [4+3] cycloadditions, reported examples were performed exclusively in an intramolecular fashions. See a) López, F.; Mascareñas, J. L. Beilstein, Beilstein J. Org. Chem. 2011, 7, 1075. b) Gulías, M.; López, F.; Mascareñas, J. L. Pure Appl. Chem. 2011, 83, 495. c) Mauleón, P.; Zeldin, R. M.; A. Z. González, Toste, F. D. J. Am. Chem. Soc. 2009, 131, 6348. d) Trillo, B.; López, F.; Montserrat, S.; Ujaque, G.; Castedo, L.; Lledós, A.; Mascareñas, J. L. Chem. Eur. J. 2009, 15, 3336. e) Alonso, I.; Faustino, H.; López, F.; Mascareñas, J. L. Angew. Chem. 2011, 123, 11698. Angew. Chem. Int. Ed. 2011, 50, 11496. f) Alonso, I.; Trillo, B.; López, F.; Montserrat, S.; Ujaque, G.; Castedo, L.; Lledós, A.; Mascareñas, J. L. J. Am. Chem. Soc. 2009, 131, 13020.
[22] see ref. 9, 10 and a) Ungureanu, I.; Klotz, P.; Mann, A. Angew. Chem. 2000, 112, 4790; Angew. Chem. Int. Ed. 2000, 39, 4615. b) Sisko, J.; Weinreb, S. M. J. Org. Chem. 1991, 56, 3210 c) Bergmeier, S. C.; Fundy, S. L.; Seth, P. P. Tetrahedron 1999, 55, 8025. d) Sugita, Y.; Kimura, Y.; Yokoe, I.; Tetrahedron Lett. 1999, 40, 5877. e) Nakagawa, M.; Kawahara, M., Org. Lett. 2000, 2, 953. f) J.-G. Shim, Y. Yamamoto, J. Org. Chem. 1998, 63, 3067. g) Yadav, J. S.; Reddy, B. V. S.; Pandey, S. K.; Srihari, P. P.; Prathap, I. Tetrahedron Lett. 2001, 42, 9089. h) Fan, J.; Gao, L.; Wang, Z. Chem. Commun. 2009, 5021.
[23] See ref. 17b and a) Inoue, M.; Sugita, T.; Kiso, Y.; Ichikawa, K. Bull. Chem. Soc. Jpn. 1976, 49, 1063. b) Nakajima, T.; Suga, S.; Sugita, T.; Ichikawa, K. Tetrahedron 1969, 25, 1807.
[24] For chemistry of ynamides, see: a) DeKorver, K. A.; Li, H.; Lohse, A. G.; Hayashi, R.; Lu, Z.; Zhang, Y.; Hsung, R. P. Chem. Rev. 2010, 110, 5064. b) Evano, G.; Coste, A.; Jouvin, K. Angew. Chem. 2010, 122, 2902; Angew. Chem. Int. Ed. 2010, 49, 2840. c) Hashmi, A. S. K.; Rudolph, M.; Huck, J.; Frey, W.; Bats, J. W.; Hamzić, M. Angew. Chem. 2009, 121, 5962; Angew. Chem. Int. Ed. 2009, 48, 5848.
[25] For gold-catalyzed electrophilic activation of ynamides, see reference [24] and selected examples: a) Li, C.-W.; Pati, K.; Lin, G.-Y.; Sohel, S. M. A.; Hung, H.-H.; Liu, R.-S. Angew. Chem. 2010, 122, 10087; Angew. Chem. Int. Ed. 2010, 49, 9891. b) Davies, P.W.; Cremonesi, A.; Martin, N. Chem. Commun. 2011, 47, 379. c) Li, C.; Zhang, L. Org. Lett. 2011, 13, 1738. d) Vasu, D.; Hung, H. H.; Bhunia, S.; Gawade, S. A.; Das, A.; Liu, R.-S. Angew. Chem. 2011, 123, 7043; Angew. Chem. Int. Ed. 2011, 50, 6911. e) Kramer, S.; Odabachian, Y.; Overgaard, J.; Rottländer, M.; Gagosz, F.; Skrydstrup, T. Angew. Chem. 2011, 123, 5196; Angew. Chem. Int. Ed. 2011, 50, 5090; f) Hashmi, A. S. K.; Bührle, M.; Wőlfle, M.; Rudolph, M.; Wieteck, M.; Rominger, F.; Frey, W. Chem. Eur. J. 2010, 16, 9846. g) Davies, P. W.; Cremonesi, A.; Dumitrescu, L. Angew. Chem. 2011, 123, 9093; Angew. Chem. Int. Ed. 2011, 50, 8931. h) Garcia, P.; Harrak, Y.; Diab, L.; Cordier, P.; Ollivier, C.; Gandon, V.; Malacria, M.; Fensterbank, L.; Aubert, C. Org. Lett. 2011, 13, 2952.
[26] Complete retention of stereochemistry has been reported for the reactions of epoxides or aziridines with CO and CO2 using low-valent metals; their mechanisms are distinct from those reactions that use Lewis acid to implement nucleophilic attack at epoxides.
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[29] a) For synthesis of ynamides see a) Dateer, R. B.; Shaibu, B. S.; Liu, R.-S. Angew. Chem. Int. Ed., 2012, 51, 113. b) Mukherjee, A.; Dateer, R. B.; Chaudhuri, R.; Bhunia, S.; Karad, S. N.; Liu, R. S. J. Am. Chem. Soc., 2011, 133, 15372. c) Yao, B.; Liang, Z.; Niu, T.; Zhang, Y. J. Org. Chem. 2009, 74, 4630. d) Schotes, C.; Mezzetti A. Angew Chem. Int. Ed. 2011, 50, 3072.
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Chapter4
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