臺灣博碩士論文加值系統

一個新穎且有效的鈀催化反應已經被開發，藉由三芳香基磷產生碳-磷鍵斷裂提供苯基，並與不同的炔類化合物進行環化加成反應。當反應物為二芳香基取代炔類時，反應會產生多取代萘環化合物，此環化加成產物是由一分子的芳香基與兩分子的炔類所構成(1：2耦合產物)。據我們所知，這是第一個經由芳香環碳-磷鍵斷裂與芳香環碳-氫鍵活化來成功合成萘環結構的例子。此外，我們也發現三芳香基磷所提供的苯基不只可以用來建構萘環骨架，也可以藉由芳香環異構化形成萘環上的芳香環取代基。
另外，當三芳香基磷與二烷基取代炔類反應時，則會生成環戊二烯衍生物27和雙環[5.3.0]癸烷衍生物30。不同種類的炔類決定著產物的化學選擇性。在此鈀催化反應下，苯基會與三分子的2-丁炔耦合得到環戊二烯衍生物。然而，與4-辛炔和5-癸炔等則會產生另一種具有位置與立體選擇性的1：2耦合產物－雙環[5.3.0]癸烷衍生物。
雖然產率不佳仍有待加強，但我們也不外乎成功地開發了一個簡單而且直接的合成方式來建構萘、雙環[5.3.0]癸烷和環戊二烯衍生物等。

New and efficient palladium-catalyzed cycloadditions of triarylphos- phines and internal alkynes have been developed. Depending on the reaction conditions and reactants, triarylphosphines provide benzo or aryl sources through the aryl C�{P bond cleavage. When diarylacetylenes were used in this reaction, highly substituted naphthalenes were furnished from a benzo unit and two molecules of alkynes. To the best of our knowledge, this is the first example for the preparation of naphthalene core by one aryl C�{P bond cleavage and one aryl C�{H bond activation. It was also observed that the benzo source for the construction of the naphthalene core can come from the aryl substitutent in diarylalkenes through an isomerization. This would lead to generate two different naphthalene cycloadducts.
In contrast, reaction of triarylphosphines with dialkylacetylenes gave cyclopentadienes 27 and/or bicycle[5.3.0]decane derivatives 30. This chemoselectivity strongly depend alkynes utilized. The former cycloadducts were formed from an aryl unit and three molecules of 2-butyne. However, 4-octyne and 5-decyne selectively enhanced the generation of bicycle[5.3.0]decanes, which were produced from an aryl unit and two molecules of an internal alkyne after dearomatization.
Although the yields are not excellent, the simplicity and straightforward method for constructing naphthalene, bicycle[5.3.0]decane, and cyclo pentadiene derivatives have been successful developed.

中文摘要................................................III
英文摘要.................................................IV
誌謝.....................................................VI
表目錄圖目錄..............................................X
壹. 前言..................................................1
貳. 結果與討論............................................8
一. 鈀催化碳�{磷鍵斷裂生成中間物 [Ag(PPh3)2]NO3...........8
二. 三芳香基磷與二芳香基炔類的環合加成反應...............11
(一) 磷化物與炔類為相同芳香基取代之化合物................13
(二) 磷化物與炔類為不同芳香基取代之化合物................16
(三) 三(2-萘基)磷化物與二芳香基炔類反應合成多取代菲環....19
三. 三芳香基磷與二烷基炔類的環合加成反應.................21
(一) 與二烷基炔類合成雙環[5.3.0]癸烷衍生物...............23
(二) 與二烷基炔類合成多取代菲環衍生物....................29
(三) 與2-丁炔合成環戊二烯衍生物..........................30
四. 三苯基磷與分子內雙炔的環合加成反應...................31
參. 結論.................................................33
肆. 實驗.................................................36
一. 合成有機磷化合物.....................................37
二. 合成產物.............................................38
伍. 參考文獻.............................................63
陸. 附錄.................................................68
一. 核磁共振光譜圖.......................................68
二. X-ray單晶繞射資料....................................96

1 Quin, L. D. A Guide to Organophosphorus Chemistry; John Wiley & Sons, 2000.
2 Garrou, P. E. Chem. Rev. 1985, 85, 171.
3 (a) Bradford, C. W.; Nyholm, R. S. J. Chem. Soc. Dalton Trans. 1973, 529. (b) Carty, A. J.; Taylor, N. J.; Smith, W. F. J. Chem. Soc. Chem. Commun. 1979, 750. (d) Foley, H. C.; Finch, W. C.; Pierpoint, C. G.; Geoffroy, G. L. Organometalhs 1982, 1 , 1379.
4 (a) Bellon, P. L.; Benedicenti, C.; Caglio, G.; Manassero, M. J. Chem. Soc. Chem. Commun. 1973, 946. (b) Lewin, M.; Aizenshtat, Z.; Blum, J. J. Organomet. Chem. 1980, 184, 255. (c) Michman, M.; Kaufman, V. D.; Nussbaum, S. J. Organomet. Chem. 1979, 182, 547.
5 (a) Coulson, D. R. J. Chem. Soc. Chem. Commun. 1968, 1530. (b) Dixon, K. R.; Rattray, A. D. Inorg. Chem. 1978, 17, 1099. (c) Nakamura, A.; Otsuka, S. Tetrahedron Lett. 1974, 463. (d) Glockling, F.; McBride, T.; Pollock, R. J. J. Chem. Soc. Chem. Commun. 1973, 650.
6 Zask, A.; Helquist, P. J. Org. Chem. 1978, 43, 1619.
7 Goel, A. B.; Richards, H. J.; Kyung, J. H. Inorg. Chim. Acta 1983, 76, L95.
8 Goel. A. B.; Richards, H. J.; Kyung, J. H. Tetrahedron Lett. 1984, 25, 391.
9 Goel, A. B. Inorg. Chim. Acta 1984, 84, L25.
10 Goel, A. B. Inorg. Chim. Acta 1984, 86, L77.
11 Kikukawa, K.; Yamane, T.; Takagi, M.; Matsuda, T. J. Chem. Soc. Chem. Commun. 1972, 695.
12 Yamane, T.; Kikukawa, K.; Takagi, M.; Matsuda, T. Tetrahedron 1973, 29. 955.
13 (a) Kikukawa, K.; Takagi, M.; Matsuda, T. Bull. Chem. Soc. Jpn. 1979, 52, 1493. (b) Kikukawa, K.; Yamane, T.; Ohbe, Y.; Takagi, M.; Matsuda, T. Bull. Chem. Soc. Jpn. 1979, 52, 1187.
14 Ryabov, A. D.; Yatsimirsky, A. K. J. Mol. Catal. 1978, 4, 449.
15 Hermann, W. A.; Broβmer, C.; Öfele, K.; Beller, M.; Fischer, H. J. Mol. Catal. 1995, 103, 133.
16 Asano, R.; Moritani, I.; Fujiwara, Y.; Teranishi, S. Bull. Chem. Soc. Jpn. 1973, 46, 2910.
17 Sakamoto, M.; Shimizu, I.; Yamamoto, A. Chem. Lett. 1995, 1101.
18 Hwang, L. K.; Na, Y.; Lee, J.; Do, Y.; Chang, S. Angew. Chem. Int. Ed. 2005, 44, 6166.
19 施建全碩士論文: 國立成功大學 民國九十六年六月。
20 (a) Stein, R. A.; Knobler, C. Inorg. Chim. 1977, 16, 242. (b) Muetterties, E. L.; Alegranti, C. W. J. Am. Chem. Soc. 1972, 94, 6386.
21 (a) Harvey, R. G. Polycyclic Aromatic Hydrocarbons; Wiley-VCH: New York, 1996. (b) Watson, M. D.; FethtenkÖtter, A.; Müllen, K. Chem. Rev. 2001, 101, 1267
22 (a) Whitesides, G. M.; Ehmann, W. J. J. Am. Chem. Soc. 1970, 92, 5625. (b) Herwig, W.; Metlesics, W.; Zeiss, H. J. Am. Chem. Soc. 1959, 81, 6203.
23 Yasukawa, T.; Satoh, T.; Miura, M.; Nomura, M. J. Am. Chem. Soc. 2002, 124, 12680.
24 Kokubo, K.; Matsumasa, K.; Miura, M.; Nomura, M. J. Org. Chem. 1996, 61, 6941.
25 (a) Sakakibara, T.; Tanaka, Y.; Yamasaki, T.-I. Chem. Lett. 1986, 797. (b) Wu, G.; Rheingold, A. L.; Feib, S. L.; Heck, R. F. Organometallics 1987, 6, 1941. (c) Tao, T.; Silverberg, L. J.; Rheingold, A. L.; Heck, R. F. Organometallics 1989, 8, 2550.
26 (a) Takahashi, T.; Hara, R.; Nishihara, Y.; Kotora M. J. Am. Chem. Soc. 1996, 118, 5154. (b) Takahashi, T.; Li, Y.; Stepnicka, P.; Kitamura, M.; Liu, Y.; Nakajima, K.; Kotora, M. J. Am. Chem. Soc. 2002, 124, 576.
27 Huang, W.; Zhou, X.; Kanno, K.�{i.; Takahashi T. Org. Lett. 2004, 6, 2429.
28 (a) Peña, D.; Escudero, S.; Pérez, D.; Guitián, E.; Castedo, L. Angew. Chem., Int. Ed. 1998, 37, 2659. (b) Peña, D.; Pérez, D.; Guitián, E.; Castedo, L. J. Org. Chem. 2000, 65, 6944. (c) Yoshikawa, E.; Radhakrishnan, K. V.; Yamamoto, Y. J. Am. Chem. Soc. 2000, 122, 7280.
29 Y.-T. Wu, K.-H. Huang, C.-C. Shin, T.-C. Wu Chem. Eur. J. 2008, 14, 6697 .
30 Satoh, T.; Ogino, S.; Miura, M.; Nomura, M. Angew. Chem. Int. Ed. 2004, 43, 5063.
31 (a) Maguire, A. R.; Buckley, N. R.; O’Leary, P.; Ferguson, G. Chem. Commun. 1996, 22, 2595. (b) Maguire, A. R.; Buckley, N. R.; O’Leary, P.; Ferguson, G. J. Chem. Soc. Perkin Trans. 1 1998, 24, 4077.
32 (a) Ye, T.; McKervey, M. A. Chem.Rev. 1994, 94, 1091. (b) Buchner, E. Ber. 1896, 29, 106.
33 (a) Reinheimer, H.; Moffat, J.; Maitlis, P. M. J. Am. Chem. Soc. 1969, 91, 2285. (b) Calvo, C.; Hosokawa, T.; Reinheimer, H.; Maitlis, P. M. J. Am. Chem. Soc. 1972, 94, 3238. (c) Hosokawa, T.; Calvo, C.; Lee, H. B.; Maitlis, P. M. J. Am. Chem. Soc. 1973, 95, 4914. (d) Hosokawa, T.; Maitlis, P. M. J. Am. Chem. Soc. 1973, 95, 4924.
34 Nakamura, M.; Miki, M.; Majima, T. J. Chem. Soc. Perkin Trans. 2 2000, 7, 1447.
35 Tim, A.; Ram G, G. Canadian Journal of Chemistry 1982, 60, 716.
36 Richter, B.; Wolf, E.d.; Koten, G. V.; Deelman, B. J. J. Org. Chem. 2000, 65, 3885.
37 Hans Albert, B.; Manfred, F.；Reinhard, H.；Guenter, S.；Helmut G, Alt. Chem. Ber. 1984, 117, 2791.
38 Stephen, F.; Frank R, H. J. Chem. Soc. Perkin Trans. 1 1980, 2233.
39 Worrall, D. E. J. Am. Chem. Soc. 1930, 52, 2933.
40 Marcel, C.；Yves, B.；Gerard, G.；Paul. T. J. Org. Chem. 1991, 56, 3537.
41 Ziegler, C. B.; Heck, R. F. J. Org. Chem. 1978, 43, 2741.
42 (a) Larock, R. C.; Tian,Q. J. Org. Chem. 2001, 66, 7372. (b) Kawasaki,
S.; Satoh, T.; Miura, M.; Nomura, M. J. Org. Chem. 2003, 68, 6836.
43 Kitamura, T.; Yamane, M.; Lnoue. K.; Todaka, M.; Fukatsu, N.; Meng, Z.; Fujiwara, Y. J. Am. Chem. Soc. 1999, 121, 11674.
44 Liu, L.; Wang, Z.; Zhao, F.; Xi, Z. J. Org. Chem. 2007, 72, 3484.
45 鄭育松碩士論文: 國立成功大學 民國九十七年七月