Revisiting the Chemistry of Superoxide: Its Roles in Organic Synthesis

Basavaraj M. Budanur; Surendra H. Mahadevegowda; Chinmay Bhat; Faiz Ahmed Khan

doi:10.1055/a-2763-2026

Synthesis, Inhaltsverzeichnis

Synthesis
DOI: 10.1055/a-2763-2026

Review

Revisiting the Chemistry of Superoxide: Its Roles in Organic Synthesis

Autor*innen

Basavaraj M. Budanur

¹Department of Chemistry, Government First Grade College Haveri, (Affiliated to Haveri University, Haveri), Haveri, India
Surendra H. Mahadevegowda

²Department of Chemistry, School of Sciences, National Institute of Technology Andhra Pradesh, Tadepalligudem, India (Ringgold ID: RIN525574)
Chinmay Bhat

³Department of Chemistry, Government First Grade College Chamarajanagar (Affiliated to University of Mysore), Chamarajanagar, India (Ringgold ID: RIN29243)
Faiz Ahmed Khan

⁴Department of Chemistry, Indian Institute of Technology, Hyderabad, India (Ringgold ID: RIN233600)

Abstract

Alle Artikel dieser Rubrik

Abstract

This review offers a comprehensive survey of the diverse chemical reactivity of the superoxide ion (O₂•⁻) in the context of organic synthesis. As a reactive oxygen species with both radical and anionic character, superoxide demonstrates remarkable versatility—acting as a Brønsted base, a nucleophile, an oxidant, and a reductant. Drawing on reported experimental and theoretical studies, we examine its roles across a range of transformations, highlighting how its reactivity varies with substrate structure and reaction medium. Special attention is given to mechanistic pathways and solvent effects, and the distinctive features of superoxide-mediated reactions compared to those involving alternative reagents. By consolidating and analyzing scattered findings from the literature, this review aims to provide a valuable reference for researchers exploring the synthetic potential of superoxide chemistry in both academic and industrial contexts.

Keywords

Reduction - Oxidation - Nucleophiles - Free radicals - Regioselectivity

Volltext

Referenzen

References
1 Neuman EW. J Chem Phys 1934; 2: 31-33
2 Haber F, Weiss J. Proc R Soc London, Ser A 1934; 147: 332-351
3 Sawyer D, Valentin J. Acc Chem Res 1981; 14: 393-400
4 Knowles PF, Gibson JF, Pick FM, Bray RC. Biochem J 1969; 111: 53-58
5 Fridovich I. Acc Chem Res 1972; 5: 321-326
6 Michelson AM, McCord JM, Fridovich I. Superoxide and Superoxide Dismutases. New York: Academic Press; 1977: 568
7 Nanni Jr EJ, Stallings MD, Sawyer DT. J Am Chem Soc 1980; 102: 4481-4485
8 Frimer AA, Gilinsky-Sharon P, Aljadeff G. et al. J Org Chem 1989; 54: 4853-4866
9 Lee-Ruff E. Chem Soc Rev 1977; 6: 195-214 https://pubs.rsc.org/en/content/articlelanding/1977/cs/cs9770600195
10 Cabelli DE. Nat Chem 2018; 10: 1173-1175
11 Chern C-I, DiCosimo R, De Jesus R, Filippo Jr JS. J Am Chem Soc 1978; 100: 7317-7327
12 Keliogg EW, Fridovich I. J Biol Chem 1977; 252: 6721-6728
13 Halliwell B. Eur J Biochem 1975; 55: 355-360
14 Hamilton GA, Libby RD, Hartzeli CR. Biochem Biophys Res Commun 1973; 55: 333-340
15 Allen JF. Biophys Res Commun 1975; 66: 36-43
16 Valentine JS, Curtis AB. J Am Chem Soc 1975; 97: 224-226
17 Sawyer DT, Roberts JL. J Electroanal Chem 1966; 12: 90-101
18 Hayyan M, Hashim MA, AlNashef IM. Chem Rev 2016; 116: 3029-3085 10.1021/acs.chemrev.5b00407
19 Johnson RA, Nidy EG. J Org Chem 1975; 40: 1680-1681
20 Sawyer DT, Gibian MJ. Tetrahedron 1979; 35: 1471-1481
21 Fridovich I. Ann Rev Pharmacol Toxicol 1983; 23: 239-257
22 Bielski BHJ, Cabelli DE. Int J Radiat Biol 1991; 59: 291
23 Johnson RA, Adrio J, Ribagorda M. Encycl Reagents Org Synth 2007; 1: 1
24 Raghuvanshi RS. Nat Volatiles Essent Oils 2020; 7: 75-82 https://www.nveo.org/index.php/journal/article/view/5093
25 Sawyer DT, Gibian MJ, Morrison MM, Seo ET. J Am Chem Soc 1978; 100: 627-628 10.1021/ja00470a046
26 Dietz R, Forno A, Larcombe EJ, Peover ME. J Chem Soc B 1970; 816-820
27 Dureja P, Casida JE, Ruzo LO. Tetrahedron Lett 1982; 23: 5003-5004
28 Singh KN, Raghuvanshi RS, Singh M. Ind J Chem 2007; 46B: 829-833 https://nopr.niscpr.res.in/handle/123456789/612
29 Budanur BM, Khan FA. Beilstein J Org Chem 2014; 10: 2531-2538
30 Khan FA, Budanur BM. Tetrahedron 2015; 71: 7600-7607
31 Le Berre A, Berguer Y. Bull Soc Chim Fr 1966; 2363: 2368
32 Merrit MV, Sawyer DT. J Org Chem 1970; 35: 2157-2159 10.1021/jo00832a011
33 Fillippo Jr JS, Chern C-I, Valentine JS. J Org Chem 1975; 40: 1678-1680 10.1021/jo00899a048
34 Danen WC, Warner RJ. Tetrahedron Lett 1977; 18: 989-998
35 Johnson RA. Tetrahedron Lett 1976; 17: 331-332
36 Corey EJ, Nicolaou KC, Shibasaki M, Machida Y, Shiner CS. Tetrahedron Lett 1975; 16: 3183-3186
37 Corey EJ, Nicolaou KC, Shibasaki M. J Chem Soc Chem Commun 1975; 658-659
38 Brimble MA, Edmonds MK, Williams GM. Tetrahedron Lett 1990; 31: 7509-7512
39 Pomeshchenko AI, Efimova IV, Dmitruk AF, Zarechnaya OM, Opeida IA. Russ J Phys Chem A 2011; 10: 1737-1741
40 Frimer A, Rosenthal I. Tetrahedron Lett 1976; 17: 2809-2812
41 Gibian MJ, Sawyer DT, Ungermann T, Tangpoonpholvivat R, Morrison MM. J Am Chem Soc 1979; 101: 640-644 10.1021/ja00497a026
42 Moro-oka Y, Foote C. J Am Chem Soc 1976; 98: 1510-1514
43 Tezuka M, Ohkatsu Y, Osa T. Bull Chem Soc Jap 1975; 48: 1471-1474
44 San Filippo JJ, Romano LJ, Chern CI, Valentine JS. J Org Chem 1976; 41: 586-588
45 San Filippo JJ, Romano LJ, Chern CI, Valentine JS. J Org Chem 1976; 41: 1077-1078
46 Rosenthal I, Frimer AA. Tetrahedron Lett 1976; 17: 2805-2808
47 Matsumoto S, Matsuo M. Tetrahedron Lett 1977; 18: 1999-2000
48 Frimer A, Rosenthal I, Hoz S. Tetrahedron Lett 1977; 18: 4631-4634
49 Kornblum N, Singaram S. J Org Chem 1979; 44: 4727-4729
50 Frimer AA, Gilinsky P. Tetrahedron Lett 1979; 20: 4331-4334
51 Crank G, Makin MIH. Tetrahedron Lett 1979; 20: 2169-2170
52 Top S, Jaouen G, McGlinchey M. J Chem Soc Chem Commun 1980; 643-644
53 Frimer AA, Gilinsky-Sharon P, Aljadeff G. Tetrahedron Lett 1982; 23: 1301-1304
54 Hae Kim Y, Chul Chung B. J Org Chem 1983; 48: 1562-1564
55 Frimer AA, Gilinsky-Sharon P, Aljadeff G, Marks V, Rosental Z. J Org Chem 1983; 48: 1700-1705
56 Stuehr DJ, Marietta MA. J Org Chem 1985; 50: 694-696
57 Matsumoto S, Matsuo M. J Org Chem 1986; 51: 1435-1440
58 Peters JW, Foote CS. J Am Chem Soc 1976; 98: 873-875
59 Blanksby S, Bierbaum V, Ellison G, Kato S. Angew Chem Int Ed 2007; 46: 4948-4950
60 Alvarez E, Francisco CG, Freire R, Hernhndez R, Salazar JA, Suhrez E. J Chem Soc Perkin Trans 1986; I: 1523-1526
61 Hae Kim Y, Chul Yoon D. Tetrahedron Lett 1988; 29: 6453-6456
62 Frimer AA, Gilinsky-Sharon P, Aljadeff G, Marks V, Rosental Z. J Org Chem 1989; 54: 4866-4872
63 Sotiriou C, Lee W, Giese RW. J Org Chem 1990; 55: 2159-2164
64 Frimer AA, Gilinsky-Sharon P. J Org Chem 1995; 60: 2796-2801
65 Sennequier N, Boucher JL, Battioni P, Mansuy D. Tetrahedron Lett 1995; 36: 6059-6062
66 Kumar R, Singh M, Singh KN. Ind J Chem Technol 1998; 5: 227-229 https://nopr.niscpr.res.in/handle/123456789/30848
67 Singh S, Singh KN. Ind J Chem Technol 2000; 7: 161-164 https://nopr.niscpr.res.in/handle/123456789/30415
68 Chen Y-J, Huang Y-P. Tetrahedron Lett 2000; 41: 5233-5236
69 Shukla AK, Singh KN. Ind J Chem Technol 2004; 11: 848-852 https://nopr.niscpr.res.in/handle/123456789/9554
70 Singh S, Verma M, Singh KN. Synth Commun 2004; 34: 4471-4475
71 Chen Y-J, Shen J-Y. Tetrahedron Lett 2005; 46: 4205-4208
72 Raghuvanshi RS, Singh KN. Ind J Chem 2008; 47B: 1735-1738 https://nopr.niscpr.res.in/handle/123456789/2549
73 Raghuvanshi RS, Singh KN. Ind J Chem 2012; 51B: 650-652 https://nopr.niscpr.res.in/handle/123456789/13834
74 Vasudevan N, Routholla G, Illa GT, Reddy DS. Tetrahedron 2020; 76: 131262
75 Jiang W, Zhang X, Sui Z. Org Lett 2002; 5: 43-46
76 Mulazzani QG, D’Angelantonio M, Venturi M, Rodgers MAJ. J Phys Chem 1991; 95: 9605-9608
77 Martin RP, Sawyer DT. Inorg Chem 1972; 11: 2644-2647
78 Wilshire J, Sawyer DT. Acc Chem Res 1979; 12: 105-110
79 Poupko R, Rosenthal I. J Phys Chem 1973; 77: 1722-1724
80 Danen WC, Arudi RL. J Am Chem Soc 1978; 100: 3944-3945
81 Ando W, Kabe Y, Kobayashi S, Takyu C, Yamagishi A, Inaba H. J Am Chem Soc 1980; 102: 4526-4528
82 Neckers DC, Hauck G. J Org Chem 1983; 48: 4691-4695
83 Gibian MJ, Russo S. J Org Chem 1984; 49: 4304-4306
84 Forrester AR, Purushotham V. J Chem Soc Perkin Trans 1987; 1: 945-948
85 Nagano T, Yamamoto H, Hirobe M. J Am Chem Soc 1990; 112: 3529-3535
86 Adam W, Asensio G, Curci R, Gonziilez-Niiiiez ME, Mello R. J Am Chem Soc 1992; 114: 8345-8349