經由金屬離子起始氧化性自由基，並加成至1,4-醌類化合物的研究，已有諸多文獻報告。藉此應用在碳-碳鍵的形成，及分子內縮合反應，可有效合成雜環化合物。我們利用此方法進行研究，論文共分為二部份:
第一部份利用銀(I)與過硫酸根離子生成的銀(II)氧化羧酸類化合物，生成醯基自由基與碳自由基；以及醋酸錳(III)與氧氣分子的系統氧化β-羰基酯化合物，生成醯基自由基。其分別與1,4-醌類化合物作用後，可獲得異呋喃-1,4-醌類化合物或異吡咯-1,4-醌類化合物。
第二部份利用醋酸錳(III)氧化丁醯乙酸乙酯，並以硝酸鈰(III)作路易士酸，與1,4-醌類化合物配位，在中性溶劑條件下可合成高產率且具選擇性的五員環及六員環產物。

The metal salts mediated radical reaction of quinones for constructing carbon-carbon bonds are described. Radical intermediates which created by Ag(II) or Mn(III) then underwent intermolecular and intramolecular cyclizations. The study was initiated by the methodolgy.
There are two parts in this thesis:
(1) Acyl and carbon radicals generated by the oxidative decarboxylation of α-ketone acid and α-amino acid respectively with silver(I) nitrate and persulfate. Besides, Acyl radicals also produced by β-ketone ester with manganese(III) and O2. Each of the radicals then underwent radical addition to 2-(1-hydroxyalkyl)-1,4-nathoquinones, 2-benzoyl-1,4-nathoquinones and 2-(1-amidoalkyl)-1,4-nathoquinones. These reactions provided effective methods for the synthesis of isofuran-1,4-nathoquinones or isopyrrole-1,4- nathoquinones.
(2) Manganese (III) acetate oxidation of ethyl butyrylacetate generated radicals which then underwent radical addition to 2-benzoyl- 1,4-benzoquinones . In the present of cerium(III) nitrate as Lewis acid, benzo[c]furan-4,7-diones and anthrancene-1,4-diones could be produced with good chemoselectivity in neutral solvent .

1.Philippe, R.; Mukund, P. S. Radicals in Organic Synthesis Volume 1: Basic Principles; WILEY-VCH, 2001, pp 1-10.
2.Snider, B. B. Chem. Rev. 1996, 96, 339.
3.Minisci, F.; Citterio, A. Acc. Chem. Res. 1983, 16, 27.
4.Bar, G.; Parson, A. F.; Thomas, C. B. Tetrahedron 2001, 4719.
5.Zhou, H.; Huang, X.; Chen, W. J. Org. Chem. 2004, 69, 5471.
6.Snider, B. B.; Patricia, J. J.; Kates, S. A. J. Org. Chem. 1988, 53, 2137.
7.Tsai, A.-I.; Wu, Y.-L.; Chuang, C.-P. Tetrahedron 2001, 57, 7829.
8.Anderson, J. M.; Kochi, J. K. J. Am. Chem. Soc. 1970, 92, 1651.
9.Citterio, A.; Gentile, A.; Minisci, F. Tetrahedron Lett. 1982, 23, 5587.
10.Citterio, A.; Franchi, V.; Minisci, F. J. Org. Chem. 1980, 45, 4752.
11.陳昱伶, 國立成功大學, 化學研究所碩士論文, 2009.
12.Piggott, M. J. Tetrahedron 2005, 61, 9929.
13.Hanumaiah, T.; Rao, G. S. R.; Rao, C. P.; Rao, K. V. J.; Cowe, H.; Cox, P. J.; Howie, R. A.; Marshall, D. S.; Thomson, R. H. Tetrahedron 1985, 41, 635.
14.Krishnakumari, G. N.; Bhuvaneswari, B.; Raja, S. I. Fitoterapia 2001, 72, 671.
15.Fotso, S.; Maskey, R. P.; Gruen-wollny, I.; Schulz, K.; Munk, M.; Laatsch, H. J. Antibiot. 2003, 56, 931–941.
16.Yano, H.; Nakanishi, S.; Matsuda, Y.; Nonomura, Y.; Sasaki, H. Anti-HIV drug; (Kyowa Hakko Kogyo Co., Ltd., Japan).Application: WO 9405283, A1 19940317, CAN 120:280309,AN 1994:280309, 1994.
17.Claessens, S.; Jacobs, J.; Aeken, S. V.; Tehrani, K. A.; Kimpe, N. D. J. Org. Chem. 2008, 73, 7555.
18.Deblander, J.; Aeken, S. V.; Jacobs, J.; Kimpe, N. D.; Tehrani, K. A. Eur. J. Org. Chem. 2009, 4882.
19.Frincke, J. M.; Faulkner, D. J. J. Am. Chem. Soc. 1982, 104, 265.
20.Kruaus, G.. A.;Man, T. O. Synth. Commun. 1986, 16, 1037.
21.Joshi, B. S.; Jiang, Q.; Rho, T.; Pelletier, S. W. J. Org. Chem. 1994, 59, 8220.
22.Cowden, C. J. Org. Lett. 2003, 5, 4497.
23.Tseng, C.-M.; Wu, Y.-L.; Chuang, C.-P. Tetrahedron 2004, 60, 12249.
24.Ritter, J. J.; Minieri, P. P. J. Am. Chem. Soc. 1948, 70, 4045.
25.Ritter, J. J.; Kalish, J. J. Am. Chem. Soc. 1948, 70, 4048.
26.Nair, V.; Nair, L. G.; Mathew, J. Tetrahedron Lett. 1998, 39, 2801.
27.Nussbaum, A. L.; Yuan, E. P.; Robinson, C. H.; Mitchell, A.; Oliveto, E. P.; Beaton, J. M.; Bartonic, D. H. R. Chem. Revs. 1959, 59, 239.
28.Chen, K.-P.; Lee, H.-Q.; Cheng, Y.-C.; Chuang, C.-P. Org. Biomol. Chem. 2009, 7, 4074.
29.蔡安益, 國立成功大學, 化學研究所博士論文, 2008.
30.林倩宇, 國立成功大學, 化學研究所碩士論文, 2004.