Synlett 2014; 25(11): 1629-1630
DOI: 10.1055/s-0034-1378210
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© Georg Thieme Verlag Stuttgart · New York

gem-Bishydroperoxides

Johannes H. van Tonder
Faculty of Natural and Agricultural Sciences, Department of Chemistry, University of the Free State, Bloemfontein 9300, South Africa   Email: vtonderjh@gmail.com
› Author Affiliations
Further Information

Publication History

Publication Date:
20 May 2014 (online)

 
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Johannes grew up in the diamond city Kimberley, South Africa. He pursued his interest in science by obtaining a B.Sc. degree in chemistry and biology in 2004 from the University of the Free State. His fondness for organic chemistry led him to procure a M.Sc. degree from the same institution in 2008. He is currently completing a Ph.D. degree under the supervision of Professor B. C. B. Bezuidenhoudt at the University of the Free State.

Introduction

The relevance of gem-dihydroperoxides to peroxidic antimalarial agents stimulated initial interest in this class of compounds.[1] [2] [3] [4] [5] Apart from their biological activities,[6,7] gem-dihydroperoxides have been established as important building blocks in synthetic chemistry, for example the preparation of organic peroxides, trioxanes, tetraoxanes, spirobisperoxyketals, and dicarboxylic diesters.[4] [7] [8] gem-Dihydroperoxides can also be employed as oxidizing agents under various conditions to perform transformations such as epoxidation[1] [2] [3] [4] [5] and sulfoxidation.[2] [3] [4] [5] [9] In addition, in situ decomposition of gem-dihydroperoxides can generate singlet oxygen as the active oxidant[8] [10] in olefin oxidation, for example.[11] The ability of gem-dihydroperoxides to generate radicals allows them to be furthermore exploited as radical initiators,[2] [3] [4] [5] for example methyl ethyl ketone peroxide is used in the manufacturing of acrylic resins, reinforced plastics, and unsaturated polyester resins.[6]

Itoh and co-workers established two catalyst-free preparative protocols for gem-dihydroperoxides, of which the one employs hydrogen peroxide[12] as terminal oxidant and the other molecular oxygen.[13] [14] The latter is achieved in combination with a photosensitizer (anthracene[13] or anthraquinone[14]) and exposure of the reaction mixture to light.

Reaction times can generally be reduced upon introduction of a catalyst, amongst which molecular iodine[15] as well as numerous transition-metal Lewis acids have proven effective.[4] [5] [8] [16] [17] Brønsted acids are comparably active as either homogeneous (sulfuric acid[3]) or heterogeneous catalysts, for example silica-sulfuric acid[2] or triflic-acid-functionalized silica-coated ferromagnetic nanoparticles.[18]


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Abstracts

(A) Dussault and co-workers[19] prepared primary and secondary alkyl hydroperoxides in moderate to high yields (48–79%) via double alkylation of 1,1-dihydroperoxides, followed by acid-catalyzed hydrolysis of the resulting strained cyclic alkylated gem-bishydroperoxides (bisperoxyacetals).

(B) 1-Hydroxy-1′-alkoxyperoxides were prepared by Terent’ev et al.[6] in moderate yield (40–64%) through iodine-catalyzed cross-coupling of gem-bishydroperoxides and acetals. This cross-coupling is also effective upon substitution of the acetal with an enol ether.

(C) Symmetrical and asymmetrical tetraoxanes can be prepared from gem-dihydroperoxides. The combination of a gem-dihydroperoxide and its carbonyl analogue in the presence of fluoroboric acid and hydrogen peroxide favors formation of symmetrical tetra­oxanes.[20] Similarly, asymmetrical tetraoxanes are obtained when two non-identical carbonyl compounds are introduced.[7]

(D) Jakka et al.[1] reported the epoxidation of various α,β-unsaturated ketones utilizing cyclohexylidene-bishydroperoxide as a stoichiometric oxidant under Weitz–Scheffer reaction conditions (aqueous, alkaline).

(E) Sulfoxidation of thiophenol ethers can be achieved under neutral conditions at ambient temperature, producing sulfoxides in high yields (79–93%) in less than two hours.[9]

(F) Subsequent to observing the oxidation of triphenylphosphine to triphenylphosphine oxide in the presence of 1,1-dihydroperoxy­cyclododecane, Sekine and co-workers[21] prepared oligodeoxyribonucleotides in a similar fashion via the oxidation of phosphite intermediates to their respective phosphate analogues.

(G) Dussault and co-workers reported the liberation of singlet oxygen when monoactivated gem-dihydroperoxide derivatives were exposed to anhydrous alkaline conditions.[22] If this degradation is performed in the presence of an organic substrate, an oxidative transformation of the substrate is observed.[10] This protocol also allows for oxidative cleavage of olefinic substrates to yield aldehydes or ­ketones in moderate to high yields (35–82%).[11]


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  • References

  • 1 Jakka K, Liu J, Zhao C.-G. Tetrahedron Lett. 2007; 48: 1395
  • 2 Azarifar D, Najminejad Z, Khosravi K. Synth. Commun. 2013; 43: 826
  • 3 Terent’ev AO, Platonov MM, Ogibin YN, Nikishin GI. Synth. Commun. 2007; 37: 1281
  • 4 Ghorai P, Dussault PH. Org. Lett. 2008; 10: 4577
  • 5 Azarifar D, Khosravi K, Soleimanei F. Synthesis 2009; 2553
  • 6 Terent’ev AO, Platonov MM, Krylov IB, Chernyshev VV, Nikishin GI. Org. Biomol. Chem. 2008; 6: 4435
  • 7 Žmitek K, Zupan M, Iskra J. Org. Biomol. Chem. 2007; 5: 3895
  • 8 Sashidhara KV, Avula SR, Singh Ravithej L, Palnati GR. Tetrahedron Lett. 2012; 53: 4880
  • 9 Jon PaulSelvam J, Suresh V, Rajesh K, Chanti BabuD, Suryakiran N, Venkateswarlu Y. Tetrahedron Lett. 2008; 49: 3463
  • 10 Hang J, Ghorai P, Finkenstaedt-Quinn SA, Findik I, Sliz E, Kuwata KT, Dussault PH. J. Org. Chem. 2012; 77: 1233
  • 11 Azarifar D, Najminejad Z. Synlett 2013; 24: 1377
  • 12 Tada N, Cui L, Okubo H, Miura T, Itoh A. Chem. Commun. 2010; 46: 1772
  • 13 Tada N, Cui L, Okubo H, Miura T, Itoh A. Adv. Synth. Catal. 2010; 352: 2383
  • 14 Cui L, Tada N, Okubo H, Miura T, Itoh A. Green Chem. 2011; 13: 2347
  • 15 Žmitek K, Zupan M, Stavber S, Iskra J. J. Org. Chem. 2007; 72: 6534
  • 16 Azarifar D, Khosravi K. J. Iran. Chem. Soc. 2012; 8: 1006
  • 17 Azarifar D, Khosravi K, Soleimanei F. Molecules 2010; 15: 1433
  • 18 Liu Y.-H, Deng J, Gao J.-W, Zhang Z.-H. Adv. Synth. Catal. 2012; 354: 441
  • 19 Kyasa S, Puffer BW, Dussault PH. J. Org. Chem. 2013; 78: 3452
  • 20 Franco LL, de Almeida MV, Rocha e Silva LF, Vieira PP. R, Pohlit AM, Valle MS. Chem. Biol. Drug Des. 2012; 79: 790
  • 21 Saneyoshi H, Miyata K, Seio K, Sekine M. Tetrahedron Lett. 2006; 47: 8945
  • 22 Ghorai P, Dussault PH. Org. Lett. 2009; 11: 4572

  • References

  • 1 Jakka K, Liu J, Zhao C.-G. Tetrahedron Lett. 2007; 48: 1395
  • 2 Azarifar D, Najminejad Z, Khosravi K. Synth. Commun. 2013; 43: 826
  • 3 Terent’ev AO, Platonov MM, Ogibin YN, Nikishin GI. Synth. Commun. 2007; 37: 1281
  • 4 Ghorai P, Dussault PH. Org. Lett. 2008; 10: 4577
  • 5 Azarifar D, Khosravi K, Soleimanei F. Synthesis 2009; 2553
  • 6 Terent’ev AO, Platonov MM, Krylov IB, Chernyshev VV, Nikishin GI. Org. Biomol. Chem. 2008; 6: 4435
  • 7 Žmitek K, Zupan M, Iskra J. Org. Biomol. Chem. 2007; 5: 3895
  • 8 Sashidhara KV, Avula SR, Singh Ravithej L, Palnati GR. Tetrahedron Lett. 2012; 53: 4880
  • 9 Jon PaulSelvam J, Suresh V, Rajesh K, Chanti BabuD, Suryakiran N, Venkateswarlu Y. Tetrahedron Lett. 2008; 49: 3463
  • 10 Hang J, Ghorai P, Finkenstaedt-Quinn SA, Findik I, Sliz E, Kuwata KT, Dussault PH. J. Org. Chem. 2012; 77: 1233
  • 11 Azarifar D, Najminejad Z. Synlett 2013; 24: 1377
  • 12 Tada N, Cui L, Okubo H, Miura T, Itoh A. Chem. Commun. 2010; 46: 1772
  • 13 Tada N, Cui L, Okubo H, Miura T, Itoh A. Adv. Synth. Catal. 2010; 352: 2383
  • 14 Cui L, Tada N, Okubo H, Miura T, Itoh A. Green Chem. 2011; 13: 2347
  • 15 Žmitek K, Zupan M, Stavber S, Iskra J. J. Org. Chem. 2007; 72: 6534
  • 16 Azarifar D, Khosravi K. J. Iran. Chem. Soc. 2012; 8: 1006
  • 17 Azarifar D, Khosravi K, Soleimanei F. Molecules 2010; 15: 1433
  • 18 Liu Y.-H, Deng J, Gao J.-W, Zhang Z.-H. Adv. Synth. Catal. 2012; 354: 441
  • 19 Kyasa S, Puffer BW, Dussault PH. J. Org. Chem. 2013; 78: 3452
  • 20 Franco LL, de Almeida MV, Rocha e Silva LF, Vieira PP. R, Pohlit AM, Valle MS. Chem. Biol. Drug Des. 2012; 79: 790
  • 21 Saneyoshi H, Miyata K, Seio K, Sekine M. Tetrahedron Lett. 2006; 47: 8945
  • 22 Ghorai P, Dussault PH. Org. Lett. 2009; 11: 4572

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