Research on Chemical Intermediates

, Volume 39, Issue 1, pp 33–42 | Cite as

Azide/oxygen photocatalysis with homogeneous and heterogeneous photocatalysts for 1,2-aminohydroxylation of acyclic/cyclic alkenes and Michael acceptors

  • Axel G. Griesbeck
  • Jörg Steinwascher
  • Melissa Reckenthäler
  • Johannes Uhlig


Homogeneous as well as heterogeneous photocatalysts that are able to oxidize the azide anion with low competitive singlet oxygen quantum yields are used to generate azidyl radicals. These radicals add to electron-rich as well as electron-poor (Michael acceptors) alkenes, and carbon radicals are formed regioselectively. Trapping with triplet oxygen (type I photooxygenation) is diffusion controlled, and the initially formed peroxy radicals are reduced with regeneration of the photocatalyst. Fluorescence quenching studies reveal rapid photoinduced electron transfer in the first catalysis step. The lack of rearrangement products in the bicyclic terpene series (pinenes, limonene) accounts for rapid subsequent oxygen trapping and back electron transfer steps. The 1,2-azidohydroperoxidation enables synthesis of 1,2-azidoalcohols and 1,2-aminoalcohols by different reduction protocols. Substrate modification and combination of type II photooxygenation with electron transfer photocatalysis allows the synthesis of 1-amino-2,3-diols and 2-amino-1,3-diols.


Photochemistry Photooxygenation Azidyl radicals Photoinduced electron transfer 



We gratefully acknowledge financial support by the Deutsche Forschungsgemeinschaft (DFG) and the Volkswagen-Stiftung.


  1. 1.
    R. Noyori, M. Aoki, K. Sato, Green oxidation with aqueous hydrogen peroxide. Chem. Commun. 16, 1977–1986 (2003)CrossRefGoogle Scholar
  2. 2.
    B.M. Trost, On inventing reactions for atom economy. Acc. Chem. Res. 35, 695–705 (2002)CrossRefGoogle Scholar
  3. 3.
    A.G. Griesbeck, M. Cho, 9-Mesityl-10-acridinium: an efficient type II and electron-transfer photooxygenation catalyst. Org. Lett. 9, 611–613 (2007)CrossRefGoogle Scholar
  4. 4.
    A. Reinheimer, R. van Eldik, H. Kisch, On the mechanism of radical C–N coupling in type B semiconductor photocatalysis: a high-pressure study. J. Phys. Chem. 104, 1014–1024 (2000)CrossRefGoogle Scholar
  5. 5.
    A.G. Griesbeck, T. Hundertmark, J. Steinwascher, Regio- and diastereoselective formation of 1,2-azidohydro-peroxides by photooxygenation of alkenes in the presence of azide anions. Tetrahedron Lett. 37, 8367–8370 (1996)CrossRefGoogle Scholar
  6. 6.
    A.G. Griesbeck, J. Lex, K.M. Saygin, J. Steinwascher, Azidohydroperoxidation of pinenes: stereoselectivity pattern and the first X-ray structure of a 2-azidohydroperoxide. Chem. Commun. 22, 2205–2206 (2000)CrossRefGoogle Scholar
  7. 7.
    A.G. Griesbeck, M. Reckenthäler, J. Uhlig, Photoinduced azidohydroperoxidation of myrtenyl hydroperoxide with semiconductor nanoparticles and lucigenin as PET-catalysts. Photochem. Photobiol. Sci. 9, 775–778 (2010)CrossRefGoogle Scholar
  8. 8.
    E. Gandin, Y. Lion, A. Van de Vorst, Quantum yield of singlet oxygen production by xanthene derivatives. Photochem. Photobiol. 37, 271–278 (1983)CrossRefGoogle Scholar
  9. 9.
    K.A. Abdullah, T.J. Kemp, Electron donor and acceptor quenching of the fluorescence of 9,10-dicyanoanthracene in polar and non-polar solvents. J. Photochem. 28, 61–69 (1985)CrossRefGoogle Scholar
  10. 10.
    D.J. Guerin, T.E. Horstmann, S.J. Miller, Amine-catalyzed addition of azide ion to α,β-unsaturated carbonyl compounds. Org. Lett. 1, 1107–1109 (1999). TMS-azide referenceCrossRefGoogle Scholar
  11. 11.
    M.S. Workentin, B.D. Wagner, J. Lusztyk, D.D.M. Wagner, Azidyl radical reactivity—N6 as a kinetic probe for the addition-reactions of azidyl radicals with olefins. J. Am. Chem. Soc. 117, 119–126 (1995)CrossRefGoogle Scholar
  12. 12.
    X.-F. Zhang, I. Zhang, L. Liu, Photophysics of halogenated fluoresceins: involvement of both intramolecular electron transfer and heavy atom effect in the deactivation of the excited states. Photochem. Photobiol. 86, 492–498 (2010)CrossRefGoogle Scholar
  13. 13.
    C.R. Lambert, I.E. Kochevar, Electron transfer quenching of the rose Bengal triplet state. Photochem. Photobiol. 66, 15–25 (1997)CrossRefGoogle Scholar
  14. 14.
    A.G. Griesbeck, L.-O. Höinck, J.M. Neudörfl, Neudörfl, Synthesis of spiroannulated and 3-arylated 1,2,4-trioxanes from mesitylol and 4-hydroxy methyltiglate by photooxygenation and peroxyacetalization. Beilstein J. Org. Chem. (2010). doi: 10.3762/bjoc.6.61 Google Scholar
  15. 15.
    A.G. Griesbeck, A. Bartoschek, J. Neudörfl, C. Miara, Stereoselectivity in ene-reactions with 1O2: matrix effects in polymer supports, photooxygenation of organic Salts and asymmetric synthesis. Photochem. Photobiol. 82, 1233–1240 (2006)CrossRefGoogle Scholar
  16. 16.
    K.A. Abdullah, T.J. Kemp, Electron-donor and acceptor quenching of the fluorescence of 9,10-dicyanoanthracence in polar and non-polar solvents. J. Photochem. 28, 61–69 (1985)CrossRefGoogle Scholar
  17. 17.
    D.W. Phillion, D.J. Kuizenga, A.E. Siegmann, Sub nanosecond relaxation time measurements using a transient induced grating method. Appl. Phys. Lett. 27, 85–87 (1975)CrossRefGoogle Scholar
  18. 18.
    B.A. Pryor, P.M. Palmer, P.M. Andrews, M.B. Berger, M.R. Topp, Spectroscopy of jet-cooled water complexes with coumarin 151: observation of vibronically induced conformational barrier crossing. J. Phys. Chem. 102, 3284–3292 (1998)CrossRefGoogle Scholar
  19. 19.
    B. Maillard, K.U. Ingold, J.C. Scaiano, Rate constants for the reactions of free radicals with oxygen in solution. J. Am. Chem. Soc. 105, 5095–5099 (1983)CrossRefGoogle Scholar
  20. 20.
    S. Bräse, C. Gil, K. Knepper, V. Zimmermann, Organic azides: an exploding diversity of a unique class of compounds. Angew. Chem. Int. Ed. 44, 5188–5240 (2005)CrossRefGoogle Scholar
  21. 21.
    W.H. Binder, C. Kluger, Azide/alkyne- “click” reactions: applications in material science and organic synthesis. Curr. Org. Chem. 10, 1791–1815 (2006)CrossRefGoogle Scholar

Copyright information

© Springer Science+Business Media B.V. 2012

Authors and Affiliations

  • Axel G. Griesbeck
    • 1
  • Jörg Steinwascher
    • 1
  • Melissa Reckenthäler
    • 1
  • Johannes Uhlig
    • 1
  1. 1.Department of ChemistryUniversity of CologneCologneGermany

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