中文摘要

本論文分成四章節，第一章主要是利用金金屬催化1,5-與1,7-丙二烯炔類分子進行水合碳環化反應之研究。第二章探討過渡金屬銀金屬催化1,5-與1,6-雙炔-3-醚類分子進行水合環化反應。第三章探討金金屬催化環氧炔類分子利用氧丙烯基陽離子進行多變的環化反應。第四章則是探討以醇醚-炔類化合物為基質，以金金屬作為催化劑，與丙烯矽烷進行雙加成反應，反應經由合環-縮環-擴環等連續步驟進行形式上的[3+2]/[2+2]環化反應，得到[3.2.0]雙環產物。
第一章利用金金屬催化劑PPh3AuCl/AgOTf催化1,5-與1,7-丙二烯炔類分子，經由水合碳環化反應得到具有化學選擇性的環狀酮類產物。此反應利用水合三鍵、分別以5-exo-trig與5-endo-trig環化過程環化，最後分子內異構化得到產物。我們利用氘元素標記實驗、對掌性轉移實驗、核對實驗以及理論計算等，針對我們所提出的π-allene活化反應機構提出佐證。
第二章利用非環狀的1,5-與1,6-雙炔醚類分子在銀金屬的催化下進行不同型態的環化反應，分別形成環丙烷酮類以及環丁烷酮類化合物，經由實驗中觀察到的結果推導其合理的反應機構。
第三章利用順式環丙烷-環氧炔類基質在AuCl3催化下，可以進行具有高度立體選擇性的環化-擴環連鎖反應，由實驗上得知順式基質的反應性與選擇性皆大於反式化合物，利用對掌性轉移實驗以及親核基加成實驗，從中了解其電子環化的反應模式。第一次環化過程中所形成的1-氧丙烯基陽離子中間體，我們更加以應用，使其與雙烯類、炔酮類、親核基、氮-氯代丁二醯亞胺，分別進行[4+2]環化加成、親核加成以及雙擴環的反應，得到多變的環狀產物，大幅增加此反應在合成上的應用性。
第四章使用金金屬催化劑AuClPPh3/AgNTf2催化4-Methoxybut-2-yn-1-ol分子與炔丙基矽烷進行形式上的[3+2]/[2+2]環化反應，得到具有高度立體選擇性的[3.2.0]環狀化合物，其反應路徑包含炔丙基取代、烯炔類分子內合環、縮環、擴環以及親核基加成等多種反應類型，一步得到天然物骨架中常見的雙環結構；此[3.2.0]環狀化合物在不同有機反應的操作下，可以得到多變的環形產物，提升了此催化反應在合成化學上的應用。

Abstract

In the first portion, we report PPh3AuCl/AgOTf-catalyzed hydrative carbocyclization of 1,5- and 1,7-allenynes to give cyclized ketones chemoselectively. In this transformation, hydration occurrs regioselectively at the C≡CPh carbon, accompanied by addition of the C≡CPh carbon to the two terminal allenyl carbons. This method is effective for the construction of a quaternary carbon center. On the basis of the chirality transfer of allenyne substrates, control experiments and theoretic calculations, we propose that this hydrative carbocyclization proceeds through an initial π-allene complex with a small energy barrier.
In the second portion, we report a new efficient silver-catalyzed hydrative carbocyclization of 1,5- and 1,6-diyne-3-methoxy acylic substrates to give cyclopropane ketone and cyclobutane ketone derivatives under ambient conditions.
In the third portion, we observed a high stereoselectivity for the AuCl3-catalyzed hydrative cyclization of 2-epoxy-1-alkynyl- cyclopropanes for the cis-epoxide isomers rather than their trans-analogues. As this cyclization produced 1-oxyallyl cation efficiently, we accomplished a two-step [4+2]-annulation of epoxylalkynes with dienes, and also with enones to provide complex oxacyclic compounds with excellent diastereoselectivity.
In the final portion, we report novel gold-catalyzed [3+2]/[2+2]-annulations of allylsilane with 4-methoxybut-2-yn-1-ols that yields highly strained bicyclo[3.2.0]heptene products efficiently and stereoselectively. Subsequent reacts with various oxidants offer additional
structural features/complexity.

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Chapter IV
1. Recent gold catalyst reviews: (a) Arcadi, A.; Giuseppe, S. D.; Curr.
Org. Chem. 2004, 8, 795. (b) Hoffmann-Röder, A.; Krause, N. Org.
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2. Irikura, K. K.; Goddard, W. A. J. Am. Chem. Soc. 1994, 116, 8733.
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Hotha, S.; Kashyap, S. J. Am. Chem. Soc. 2006, 128, 9620. (d) Liu, Y.;
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Barluenga, J.; Diéguez, A.; Fernández, A.; Rodriguez, F.; Fañanás, F. J.
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4. Nitrogen and Sulfur nucleophlies addition selected example: (a)
Alfonsi, M.; Arcadi, A.; Aschi, M.; Bianchi, G.; Marinelli, F. J. Org.
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J.-W.; Shin, S. Org. Lett. 2006, 8, 3537. (d) Nakamura, I.; Sato, T.;
Yamamoto, Y. Angew. Chem. Int. Ed. 2006, 45, 4473. (e) Arcadi, A.;
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5. Carbon nucleophiles addition selected example: (a) Nieto-Oberhuber,
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C.; López, S.; Muñoz, M. P.; Jiménez-Núñez, E.; Buñuel, E.; Cárdenas,
D. J.; Echavarren, A. M. Eur. J. Org. Chem. 2006, 11, 4555. (b) Zang,
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813. (d) Mendez, M.; Mamane, V.; Fürstner, A. Chemtracts, 2003, 16,
397. (e) Diver, S. T.; Giessert, A. J. Chem. Rev. 2004, 104, 1317.
7. Madhushaw, R.; Lo, C.-Y.; Hwang, C.-W.; Su, M.-D.; Shen, H.-C.;
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8. (a) Fürstner, A.; Szillat, H.; Stelzer, F. J. Am. Chem. Soc. 2000, 122,
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N.; Inoue, H.; Kotsuma, T.; Murai, S. J. Am. Chem. Soc. 2002, 124,
10294. (d) Nieto-Oberhuber, C.; Munoz, P. M.; Bunuel, E.; Nevado,
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9. Li, G.; Huang, X.; Zhang, L. J. Am. Chem. Soc. 2008, 130, 6944
10. (a) Kashiwabara, M.; Kamo, T.; Makabe, H.; Shibata, H.; Hirota, M.
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11. For gold-catalyzed intermolecular cycloaddition reactions, : (a)
Shapiro; N. D.; Shi, Y.; Toste, F. D. J. Am. Chem. Soc., 2009, 131,
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130, 6944; (f) Zhang, G.; Huang, X.; Li, G.; Zhang, L. J. Am. Chem.
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N. D.; Toste, F. D. J. Am. Chem. Soc. 2008, 130, 9244; (i) Schelwies,
M.; Dempwolff, A. L.; Rominger, F.; Helmchen, G. Angew. Chem.
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12. Reviews for the reactions of allylsilane, see reviews: (a) Chabaud, L.;
James, P.; Landais, Y. Eur. J. Org. Chem. 2004, 3173; (b) Masse, C.
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In Main Group Metals in Organic Synthesis; H. Yamamoto, K.
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13. Selected examples for the annulations of allylsilanes, see: (a) Keck, G.
E.; Covel, J. A.; Schiff, T.; Yu, T. Org. Lett. 2002, 4, 1189; (b)
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14. Chabaud, L.; James, P.; Landais, Y. Eur. J. Org. Chem. 2004, 3173.
15. Masse, C. E.; Panek, J. S. Chem. Rev. 1995, 95, 1293.
16. Keck, G. E.; Covel, J. A.; Schiff, T.; Yu, T. Org. Lett. 2002, 4, 1189.
17. Tinsley, J. M.; Mertz, E.; Chong, P. Y.; Rarig, R.-A. F.; Roush, W. R.
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18. Franz, A. K.; Dreyfuss, P. D.; Schreiber, S. L. J. Am. Chem. Soc. 2007,
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19. Restorp, P.; Fischer, A.; Somfai, P. J. Am. Chem. Soc. 2006, 128,
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20. Yang, D.; Micalizio, G. J. Am. Chem. Soc. 2009, 131, 17548.
21. (a) Lin, C.-C.; Teng, T.-M.; Tsai, T.-C.; Liao, H.-Y.; Liu, R.-S. J. Am.
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22. (a) Hsu, Y.-C.; Ting, C.-M.; R.-S. Liu, J. Am. Chem. Soc. 2009, 131,
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23. Derivatives of 2-butyn-1,4-diols were previously used in
gold-catalyzed cyclization without external nucleophiles, see: Buzas,
A.; Istrate, F.; Gagosz, F. Org. Lett. 2006, 8, 1957.
24. (a) Boucard, M. V.; Campagne, J.-M. J. Am. Chem. Soc. 2005, 127,
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25. Leading references for gold catalyzed 1,n-enyne cycloisomerizations,
see: (a) Jiménez-Nứňez, E.; Echavarren, A. M. Chem. Rev. 2008, 108,
3326; (b) Jiménez-Nứňez, E.; Echavarren, A. M. Chem. Commun.
2007, 333; (c) Zhang, L.; Sun, J.; Kozmin, S. A. Adv. Synth. Catal.
2006, 348, 2271; (d) Fürstner, A.; Davies, P. W. Angew. Chem. 2007,
119, 3478; Angew. Chem. Int. Ed. 2007, 46, 3410; (e) Gorin, D. J.;
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6306; (d) Mézailles, N.; Ricard, L.; Gagosz, F. Org. Lett. 2005, 7,
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