本篇論文主要是研究芳香基（aryl）碘化合物與醛類之間的偶合反應。在催化量的Ni(dppe)Br2與鋅粉存在下，我們利用Ni(0)來催化芳香碘化合物與醛類。在溫度為110℃時，以THF為溶劑，所得到酮類化合物其產率介於38-87%，一般而言，芳香醛化合物所得到的產率較脂肪(aliphatic)醛來的高。此類的偶合反應與所使用的磷（phosphine）配位基有著密不可分的關係，而且在實驗過程中發現，雙牙基的配位子是造成此催化反應能夠成功進行的重要因素之一。探討其反應機構，反應中最重要的步驟似乎是從鎳上的芳香基移到醛類羰基（carbonyl）上的碳，之後伴隨著b-氫的離去(b-hydride elimination)反應得到酮類。此外，氫氣的偵測對整個反應機構的推導幫助也很大。此反應是具醛類選擇性，且所得到的酮類可具有多樣性的官能基，如：鹵素、酮類、酯類等。
此外，溫度及溶劑對反應的影響也很重要。我們分別嘗試了不同的反應條件，結果發現溫度為110℃，反應時間為24-36小時，溶劑為THF，所得到的產率最高。我們也嘗試能完成分子內環化反應，來得到產物1-indanone或1-indanol，但產率並不理想。

我們希望第一次報導這種鎳催化芳香碘化合物與醛類偶合的方法，並且能夠得到相對應具高度化學選擇性的酮類。

參考文獻
1.(a)Crabtree, R. H. The Organometallic Chemistry of the
Transition Metals; John Wiley & Sons, Inc: New York 1994, p329.
(b)Iqbal, J.; Bhatia, B.; Nayyar, N. K., Chem. Rev. 1994, 94 ,519.
2.Jolly, P. Comprehensive Organometallic Chemistry, vol 8, Eds. Wilkinson, G.; Stone, F. G. A.; Abel, E. W., Pergamon Press, Oxford 1982.
3.Jolly, P. W.; Wilke, G. The Organic Chemistry of Nickel, Vol I, II, Academic Press, New York, 1974, 1975.
4.Heck, R. F., Palladium Reagents in Organic Synthesis, Academic Press, New York, 1978.
5.Maitlis, P. M., The Organic Chemistry of Palladium, Vol I, II, Academic Press, New York 1971.
6.(a)Colon, I.; Kelsey, D. R. J. Org. Chem. 1986, 51, 2627.
(b)Takagi, K.; Hayama, N.; Inokawa, S. Bull. Chem. Soc. Jpn. 1980, 53, 3691.
(c)Takagi, K.; Hayama, N. Chem. Lett. 1983, 3691.
(d)Iyoda, M.; Sakaitani, M.; Miyazaki, T.; Oda, M. Chem. Lett. 1984, 2005.
7.Brunet, J. J.; Besazzi, D.; Courtois, A.; Caubere, P. J. Am. Chem. Soc. 1982, 104, 7030.
8.(a)Kavaliunas, A. V.; Taylar. A.; Rieke, R. D. Organometallic 1983, 2, 377.
(b)Inaba, S.; Rieke, R. D. Synthesis 1984, 844.
9.(a)Donda, A. F.; Moretti, G. J. Organomet. Chem. 1966, 31, 985.
(b)Luttinger, L. B. J. Org. Chem. 1962, 27, 1591.
(c)Chini, P.; Santambrogio, A.; Palladino, N. J. Chem. Soc., C 1967, 830.
(d)Chini, P.; Palladino, M.; Santambrogio, A. J. Chem. Soc., C 1967, 836.
(e)Pasquale, R. J. J. Organomet. Chem. 1971, 32, 381.
(f)Luttinger, L. B.; Colthup, E. C. J. Org. Chem. 1962, 27, 3752.
(g)Luttinger, L. B. Chem. Ind. 1960, 1135.
(h)Boston, J. L.; Sharp, D. W. A.; Wilkinson, G. J. Chem. Soc. 1962, 3488.
10.(a)Onsager, O. T.; Wang, H.; Blindheim, U. Helu. Chim. Acta. 1969, 52, 187.
(b)Onsager, O. T.; Wang, H.; Blindheim, U. Helv. Chim. Acta 1969, 52, 215.
(c)Onsager, O. T.; Wang. H.; Blindheim, U. Helv. Chim. Acta 1962, 52, 230.
(d)Chauvin, Y.; Phung, H. H.; Guichard-Louder, N.; Lefebvre, G. Bull. Soc. Chim. Fr. 1996, 3233.
(e)Eberhardt, G. G.; Griffin, W. P. J. Catal. 1970, 16, 245.
11.Sakakibara, M.; Takahashi, Y.; Sakai, S.; Ishii, Y. J. Chem. Soc. Chem. Commun. 1969, 396.
12.Moberg, C. Tetrahedron Lett. 1981, 22, 4827.
13.(a) Sonogashira, K.; Tohda, Y.; Hagihara, N. Tetrahedron Lett. 1975, 4467.
(b)Tahahashi, S.; Kuroyama, T.; Sonogashira, K.; Hagihara, N. Synthesis 1986, 627.
(c)Robius, M. J.; Barr, P. J. Tetrahedron Lett. 1981, 22, 421.
(d)Kasahara, A.; Izami, T.; Maemura, M. Bull. Chem. Soc. Jpn. 1977, 50, 1021.
14.Lukes, J. H.; Blom, J. E. J. Organomet. Chem. 1971, 26, C25.
15.國立清華大學李進送博士論文.
16.Nahm, S.; Weinreb, S. M. Tetrahedron Lett. 1981, 22, 3815.
17.Prasad, J. S.; Liebeskind, L. S. Tetrahedron Lett. 1987, 28, 1857.
18.Araki, M.; Sakata, S.; Takei, H.; Mukaiyama, T. Bull. Chem. Soc. Jpn. 1974, 47, 1777.
19.Rubottom, G. M.; Kim, C. J. Org. Chem. 1983, 48. 1550.
20.Cooke, jr. M. P.; J. Org. Chem. 1986, 51, 3517.
21.Parham, W. E.; Bradsher, C. K. Acc. Chem. Res. 1982, 15,300.
22.(a)Knudesn, C. G.; Rapoport, H. J. Org. Chem. 1983, 48, 2260.
(b)Buckley, T. F.; Rapoport, H. J. Am. Chem. Soc. 1981, 103, 6157.
23.Dieter, R. K.; D. M. 1975, 3375. Tetrahedron Lett. 1999, 55, 4177.
24.Bal, S. A.; Marfat, A.; Helquist, P. J. Org. Chem. 1982, 47, 5045.
25.Ritter, K.; Hanack, M. Tetrahedron Lett. 1985, 26, 1285.
26.Kikkawa, I.; Yorifuji, T. Synthesis 1980, 877.
27.(a) Fehr, C. Galingo, J. Helv. Chim. Acta.1986, 69, 228.
(b) Fehr, C. Galingo, J. J. Org. Chem. 1988, 53, 182828.(a)Corey, E. J.; Dawson, R.; J. Am. Chem. Soc. 1962, 84, 4899.
(b)Sakan T.; Mori Y. Chem. Lett. 1972, 793.
29.(a)Meyers, A. I.; Comins, D. L. Tetrahedron Lett. 1978, 5179.
(b)Comins, D. L.; Meyers, A. I. Synthesis 1978, 403.
30.Kende, A. S.; Scholz, D.; Schneider, J. Synth. Commun. 1978, 8, 59.
31.Fujisawa, T.; Iida, S.; Uehara H.; Sato. A. Chem. Lett. 1983, 1267.
32.Whitesides, G. M.; Casey, C. P.; San Filippo, jr. J.; Panek, E. J. N.Y. Acad. Sci. 1967. 29. 572.
33.(a)Wehmeyer, R. M.; Rieke, R. D. Tetrahedron Lett. 1988, 29, 4513.
(b)Ebert, G. W.; Rieke, R. D. J. Org. Chem. 1988, 53, 4482.
34.Marfat, A.; McGuirk, P. R.; Helquist, P. Tetrahedron Lett. 1978, 1363.
35.(a)Marfat, A.; McGuirk, P. R.; Kramer R. Helquist, P. J. Am. Chem. Soc. 1977, 99, 253 and references cited therein
(b)Normant, J. F.; Cahiez, G. Bourgain, M.; Chuit C.; Villieras, J.; Bull. Sec. Chim. Fr. 1974, 1656.
(c)Alexakis, A.; Normant, J. F.; Villieras, J. Tetrahedron Lett. 1976, 3461.
(d)Westmijze, H.; Kleijn H.; Vermeer, P. Tetrahedron Lett. 1977, 2023.
36.Jabri, N.; Alexakis, A.; Normant, J. F. Tetrahedron Lett. 1983, 24, 5081.
37.(a) For recent discussion of organocuprate preparation see (a) Posner, G. H.; 'An Introduction to Synthesis Using Organocopper Reagents', Wiley, New York, 1980.
(b)Lipshutz, B. H. Synthesis 1987, 325.
(c)Lipshutz, B. H.; Wilhelm R. S.; Kozlowski, J. A. Tetrahedron 1984, 40, 5005.
(d)Noltes, J. G.; van Koten, G. in 'Comprehensive Organometallic Chemistry', ed Wilkinson, G.; Stone F. G. A.; Abel, E. W. Pergamon Press, Oxford, 1982, vol. 2, p. 709; Carruthers, W. vol. 7, p. 685.
(e)Bertz, S. H.; Gibson, C. P.; Dabbagh, G. Tetrahedron Lett. 1987, 4251.
(f)Lipshutz, B. H.; Whitney, S.; Kozlowski, J. A.; Breneman C. M. Tetrahedron Lett. 1986, 4273 and references cited therein.
38.Posner, G. H.; Whitten C. E.; McFarland. P. E. J. Am. Chem. Soc. 1972, 94, 5106.
39.Fex, T.; Froborg,J.; Magnusson, G.; Thoren, S. J. Org. Chem. 1976, 41, 3518. Treatment of the diketone with base readily effected epimerization, which was followed by condensation to theα,β-unsaturated bicyclic ketone.
40.Posner G. H.; and Whitten C. E. Org. Synth. 1976, 55, 122
41.(a) Knochel, P.; Yeh, M. C. P. ; Berk , S. C.; Talbert, J. J. Org. Chem. 1988, 53, 2392.
(b)Yeh, M. C. P.; Knochel, P. Tetrahedron Lett. 1988, 29, 2395.
(c)Yeh, M. C. P.; Knochel, P.; Santa, L. E. Tetrahedron Lett. 1988, 29, 3887.
42.Kim, S.; Lee J. I. Chung. B. Y. J. Chem. Soe., Chem. Commun. 1981, 1231.
43.(a)Kim, S.; Lee J. I. J. Org. Chem. 3983, 48, 2608.
(b)Kim, S. Org. Prep. Proced. Int. 1988, 20, 145.
44.For a review of Ni and Pd catalyzed coupling reactions see: Negishi, E. Acc. Chem. Res. 1982, 15, 340.
45.For a review of palladium chemistry see: Hegedus, L. S. Palladium in Organic Synthesis In "Organometallics in Synthesis: A Manual", Schlosser, M., Ed.: John Wiley & Sons: UK, 1994; Chapter 5, p382.
46.Amatore, C.; Jutand, A.; Suarez, A. J. Am. Chem. Soc. 1993, 115, 9531.
47.Dieter, R. K.: Li, S. J. Org. Chem. 1997, 62, 7726.
48.Cho. C. S.; Itotani, K.; Uemura, S. J. Organomet. Chem. 1993, 443, 253-259.
49.Kosugi M.; Shimizu Y.; Migita T. Chem.Lett. 1977, 1423.
50.(a)Milstein D.; Stille J. K. J. Am. Chem. Soc. 1978, 100, 3636.
(b)Milstein D.; Stille J. K. J. Org. Chem. 1979, 144, 1613.
(c)Stille J. K. Angew. Chem., Int. Ed. Engl. 1986. 25. 508.
51.Liebeskind, L. S.; Stone, G. B.; Zhang, S. J. Org. Chem. 1994, 59, 7917.
52.Arukwe, J.; Undheim, K. Acra. Chem. Scand. 1991, 45, 914.
53.Salituro, F. G.; McDonald, I. A. J. Org. Chem. 1988, 53, 6138.
54.Negishi, E.; Bagheri V.; Chatterjee S.; Luo, F-. T.; Miller, J. A.; Stoll, A. T. Tetrahedron Lett. 1983, 24, 5181.
55.Tamaru, Y.; Ochiai, H.; Sanda, F.; Yoshida, Z. Tetrahedron Lett. 1985, 26, 5529.
56.Larock, R. C.; Bernhardt, J. C. J. Org. Chem. 1978, 43, 710.
57.Wakamatsu K.; Okuda, Y.; Oshima, K.; Nozaki, H. Bull. Chem. Soc. Jpn. 1985, 58, 1425.
58.Onaka M.; Matsuoka, Y.; Mukaiyama T. Chem. Lett. 1981, 531.
59.(a)Hudlicky, M. In Oxidations in Organic Chemistry; Ed.; ACS Monograph 186; American Chemical Society: Washington, DC, 1990.
(b)Larock, R. C. In Comprehensive Organic Transformations; VCH: New York, 1989; p 591.
60.(a)Olah, G. In Friedel-Crafts and Related Reactions; Interscience Publishers: New York, 1964; Vol. III, p 1259.
(b)Osman, M. Helv. Chim. Acta 1982, 65, 2448.
(c)Zimmerman, H. E.; Paskovich, D. H. J. Am. Chem. Soc. 1964, 86, 2149.
(d)Heitzler, F. R.; Hopf, H.; Jones, P. G.; Bubenitschek, P.; Lehne, V. J. Org. Chem. 1993, 58, 2781.
61.(a)Cardellicchio, C.; Fiandanese, V.; Marchese, G.; Ronzini, L. Tetrahedron Lett. 1987, 28, 2053.
(b)Malanga, C; Aronica, L. A.; Lardicci, L. Tetrahedron Lett. 1995, 36, 9185.
62.(a)Haddach, M; MaCarthy, J. R. Tetrahedron Lett. 1999, 40, 3109.
(b)Bumagin, N. A.; Korolev, D. N. Tetrahedron Lett. 1999, 40, 3057.
(c)Kabalka, G. W.; Malladi, R. R.; Tejedor, D.; Kelley, S. Tetrahedron Lett. 2000, 41, 999 and references cited therein.
63.(a)Ishiyama, T.; Kizaki, H.; Hayashi, T.; Suzuki, A.; Miyaura, N. J. Org. Chem. 1998, 63, 4726.
(b)Ishiyama, T.; Kizaki, H.; Miyaura, N.; Suzuki, A. Tetrahedron Lett. 1993, 34, 7595.
64.(a)Hirao, T.; Misu, D.; Agawa, T. J. Am. Chem. Soc. 1985, 107, 7179.
(b)Satoh, T.; Itaya, T.; Miura, M.; Nomura, M. Chem. Lett. 1996, 823.
65.(a)Kong, K. -C.; Cheng, C. -H. J. Chem. Soc., Chem. Commun. 1991, 423.
(b)Kong, K. -C.; Cheng, C. -H. Organometallics 1992, 11, 1972.
(c)Feng, C. -C.; Nandi, M.; Sambaiah, T.; Cheng, C. -H. J. Org. Chem. 1999, 64, 3538.
(d)Sambaiah, T.; Li, L. P.; Huang D. J.; Lin, C. H.; Rayabarapu, D. K.; Cheng, C. -H. J. Org. Chem. 1999, 64, 3663.
(e)Sambaiah, T.; Huang, D. J.; Cheng, C. -H. J. Chem. Soc. Perkin Trans 1 2000, 195.
66.Ishiyama, T.; Hartwig. J. J. Am. Chem. Soc. 2000, 122, 12043.
67.Majumdar, K. K.; Cheng, C. -H. Org. Lett. 2000, 2, 2295.
68.(a) Semmelhack, M. F.; Helquist, P.; Jones, L. D.; Keller, L.; Mendelson, L.; Ryono, L. S.; Smith, J. G.; Stauffer, R. D. J. Am. Chem. Soc. 1981, 103, 6460.
(b)Yamamoto, T.; Wakabayashi, S.; Osakada, K. J. Organomet. Chem. 1992, 428, 223.
69.Tanaka, K.; Kishigami, S.; Toda, F. J. Org. Chem. 1990, 55, 2981.
70.Gibsons, S. E.; Guillo, N.; Middleton R. J.; Thuilliez, A.; Tozer, M. J. J. Chem. Soc.; Perkin Trans 1, 1997, 447.
71.Ikeda, S.; Sato, Y. J. Am. Chem. Soc. 1994, 116, 5975.