Journal of Photoscience

Korean Society of Photoscience (한국광과학회)
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Explorative and Mechanistic Studies of the Photooxygenation of Sulfides

  • Albini, Angelo (Department of Organic Chemistry, University of Pavia) ;
  • Bonesi, Sergio M. (Department of Organic Chemistry, University of Pavia)
  • Published : 2003.04.01
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Abstract

The results of recent work on the dye-sensitized photooxygenation of sulfides is discussed. In the case of dialkyl sulfides, the weakly bonded adduct initially formed with singlet oxygen (the persulfoxide) decays unproductively unless protonation by an acid (an alcohol or a carboxylic acid) facilitates its conversion to the sulfoxide. The effect is proportional to the strength of the acid (eg., less than 0.1 % chloroacetic acid in benzene is sufficient for maximal efficiency) and corresponds to general acid catalysis, suggesting that protonation of the persulfoxide occurs. On the other hand, with sulfides possessing an activated hydrogen in ${\alpha}$ position (eg., benzyl and allyl sulfides), hydrogen transfer becomes an efficient process in aprotic media and yields a S-hydroperoxysulfoniumm ylide, possibly arising from a conformation of the persulfoxide that is different from the one protonated in the presence of acids. Calculations on some substituted sulfides support this hypothesis. This process, which leads to C-S bond fragmentation with formation of an aldehyde, may be viewed as a general method for the preparation of aryl and heteroaryl aldehydes. In this effort, mechanistic studies offered new hints on the structure of the intermediate persulfoxide.

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References

  1. Singlet Oxygen Quenching of singlet oxygen Foote,C.S.;Wasserman,H.H.(ed.);R.W.Murray(ed.)
  2. Sulfur Rep. v.1 Photooxidation of organosulfur compounds Ando,W.
  3. Adv. Photochem. v.17 The biomolecular reaction of singlet oxygen Gorman,A.A.
  4. Sulfur Rep. v.19 The reaction of sulfides and sulfenic acid derivatives with singlet oxygen Clennan,E.L.
  5. Acc. Chem. Res. v.34 Persulfoxide: key intermediate in the reaction of singlet oxygen with sulfides Clennan,E.L.
  6. J. Am. Chem. Soc. v.105 Chemistry of singlet oxygen 45. Mechanism of the photooxidationn of sulfides Liang,J.J.;C.L.Gu;C.S.Foote
  7. J. Org. Chem. v.57 Remote participation during photooxidation of sulfides. Evidence for sulfurane intermediates Clennan,E.L.;K.Yang
  8. J. Am. Chem. Soc. v.119 Experimental and ab initio computational evidence of a new peroxidation intermediate (iminopersulfenic acids). Substituent effect in the photooxidations of sulfenic acid derivatives Greer,A.;M.F.Chen;F.Jensen;E.L.Clennan
  9. J. Am. Chem. Soc. v.120 Reaction of organic sulfides with singlet oxygen. A revised mechanism Jensen,F.;A.Greer;E.L.Clennan
  10. J. Am. Chem. Soc. v.120 A theoretic study of unimolecular reactions of dimethylpersulfoxide McKee,M.L.
  11. Tetrahedron v.53 Photoinduced electron transfer reactions of benzyl phenyl sulfides promoted by 9, 10-dicyanoanthracene Baciocchi,E.;C.Crescenzi;O.Lanzalunga
  12. J. Org. Chem. v.65 Effect of protic cosolvents on the photooxygenation of diethyl sulfide Bonesi,S.M.;A.Albini
  13. J. Am. Chem. Soc. v.61 Effect of alcohols on the photooxidative behavior of diethyl sulfide Clennan,E.L.;A.Greer
  14. J. Chem. Ed. v.63 Catalysis of photochemical reactions. Opportunities and pitfalls Albini,A.
  15. Tetrahedron Lett. Intermediates in the oxidation of benzyl alkyl sulfides by singlet oxygen Corey,E.J.;C.Ouannes
  16. J. Am. Chem. Soc. v.113 Cooxidation reaction in the singlet oxygenation of cyclic and benzylic sulfides. S-hydroperoxysulfonium ylide intermediate as a new epoxidizing species Akasaka,T.;A.Sakurai;W.Ando
  17. J. Org. Chem. v.63 Photosensitized oxygenation of benzyl ethyl sulfide Bonesi,S.M.;M.Mella;N.d'Alessandro;G.G.Aloisi;M.Vanossi;A.Albini
  18. J. Phys. Org. Chem. v.12 Photosensitized oxgenation of some benzyl sulfides. The role of persulfoxide Bonesi,S.M.;M.Freccero;A.Albini
  19. Eur. J. Org. Chem. The photooxygenation of benzyl, heteroarylmethyl, and allyl sulfides Bonesi,S.M.;R.Torriani;M.Mella;Albini,A.