Research on Chemical Intermediates

, Volume 38, Issue 3–5, pp 847–862 | Cite as

A strategy for the preparation of cyclic polyarenes based on single electron transfer-promoted photocyclization reactions



Single electron transfer (SET)-promoted photocyclization reactions of substrates comprised of benzylsilane tethered to phthalimides were subjected to an exploratory study in order to probe a new approach for the preparation of cyclic polyarenes. The results show that UV irradiation of the substrates leads to efficient photochemical reactions that are initiated by SET from benzylsilane moieties to the excited phthalimide acceptor. Ensuing desilylation reactions of the benzylsilane cation radical moieties in the intermediate zwitterionic biradicals and proton transfer gives biradical precursors of the cyclic polyarene products. The observations made in this effort suggests that SET photochemical methods, which have been employed earlier to generate cyclic poly-ethers, -thioethers and -amides, serve as a useful method to access potentially interesting macrocyclic targets.


SET photochemistry Cyclic polyarenes Benzylsilanes Phthalimides 



This investigation was supported financially by the National Research Foundation of Korea Grant to U.C.Y. supported by the Korean Government (KRF-2008-521-C00156). In addition, we offer our congratulation to Professor Kazuhiko Mizuno on the excellent career he has had in the academic profession and for the important scientific contributions he has made to the fields of organic chemistry and organic photochemistry.


  1. 1.
    R.A. Marcus, On the theory of oxidation-reduction reactions involving electron transfer I. J. Chem. Phys. 24, 966–972 (1956)CrossRefGoogle Scholar
  2. 2.
    D. Rehm, A. Weller, Kinetics of fluorescence quenching by electron transfer and H-atom transfer. Isr. J. Chem. 8, 259–269 (1970)Google Scholar
  3. 3.
    R.A. Neunteufel, D. Arnold, Radical ions in photochemistry. I. The 1,1-diphenylehthylene cation radical. J. Am. Chem. Soc. 95, 4080–4081 (1973)CrossRefGoogle Scholar
  4. 4.
    H.E. Zimmerman, Five decades of mechanistic and exploratory organic photochemistry. Pure Appl. Chem. 78, 2193–2203 (2006)CrossRefGoogle Scholar
  5. 5.
    K. Mizuno, M. Ikeda, Y. Otsuji, A novel photosubstitution of dicyanobenzenes by allylic and benzylic silanes. Tetrahedron Lett. 26, 461–464 (1985)CrossRefGoogle Scholar
  6. 6.
    K. Mizuno, T. Hayamizu, H. Maeda, Regio- and stereoselective functionalization of electron-deficient alkenes by orgaosilicon compounds via photoinduced electron transfer. Pure Appl. Chem. 75, 1049–1054 (2003)CrossRefGoogle Scholar
  7. 7.
    K. Ohga, P.S. Mariano, Electron transfer initiated photoaddition of allylsilanes to 1-methyl-2-phenylpyrrolinium perchlorate. A novel allylation methodology. J. Am. Chem. Soc. 104, 617–619 (1982)CrossRefGoogle Scholar
  8. 8.
    K. Ohga, U.C. Yoon, P.S. Mariano, Exploratory and mechanistic studies of the electron-transfer-initiated photoaddition reactions of allylsilane-iminium salt systems. J. Org. Chem. 49, 213–219 (1984)CrossRefGoogle Scholar
  9. 9.
    R.M. Borg, R.O. Heuckeroth, A.J.Y. Lan, S.L. Quillen, P.S. Mariano, Arene iminium salt electron transfer photochemistry. Mechanistically interesting photoaddition processes. J. Am. Chem. Soc. 109, 2728–2737 (1987)CrossRefGoogle Scholar
  10. 10.
    A.J.Y. Lan, R.O. Heuckeroth, P.S. Mariano, Electron transfer induced photocyclization reactions of arene-iminium salt systems. Effects of cation radical deprotonation and desilylation on the nature and efficiencies of reaction pathways followed. J. Am. Chem. Soc. 109, 2738–2745 (1987)CrossRefGoogle Scholar
  11. 11.
    X. Lin, R.W. Kavash, P.S. Mariano, Two interrelated strategies for cephalotaxine synthesis. J. Org. Chem. 61, 7335–7347 (1996)CrossRefGoogle Scholar
  12. 12.
    D.H. Ho, P.S. Mariano, Exploratory, mechanistic and synthetic aspects of silylarene-iminium salt set photochemistry. Studies of diradical cyclization processes and applications to protoberberine alkaloid synthesis. J. Org. Chem. 53, 5113–5127 (1988)CrossRefGoogle Scholar
  13. 13.
    U.C. Yoon, S.W. Oh, J.H. Lee, J.H. Park, K.T. Kang, P.S. Mariano, Applications of phthalimide photochemistry to macrocyclic polyether, polythioether and polyamide synthesis. J. Org. Chem. 66, 939–943 (2001)CrossRefGoogle Scholar
  14. 14.
    U.C. Yoon, Y.X. Jin, S.H. Oh, C.H. Park, J.H. Park, C.F. Campana, X. Cai, E.N. Duesler, P.S. Mariano, A synthetic strategy for the preparation of cyclic peptide mimetics based on set-promoted photo-cyclization processes. J. Am. Chem. Soc. 125, 10664–10671 (2003)CrossRefGoogle Scholar
  15. 15.
    U.C. Yoon, P.S. Mariano, The synthetic potential of phthalimide photochemistry. Acc. Chem. Res. 34, 523–533 (2001)CrossRefGoogle Scholar
  16. 16.
    D.W. Cho, U.C. Yoon, P.S. Mariano, Studies leading to the development of a single electron transfer photochemical strategy for the synthesis of macrocyclic polyethers, polythioethers and polyamides. Acc. Chem. Res. 44, 204–215 (2011)Google Scholar
  17. 17.
    U.C. Yoon, S.W. Oh, C.W. Lee, Efficient and regioselective photocyclization reactions of N-trimethylsilyl-methoxy) polyoxalkyl phthalimides to azacrown ethers. Heterocycles 41, 2665–2682 (1995)CrossRefGoogle Scholar
  18. 18.
    D.W. Cho, J.H. Choi, S.W. Oh, C. Quan, U.C. Yoon, R. Wang, S. Yang, P.S. Mariano, Single electron transfer promoted photocyclization reactions of linked acceptor-polydonor systems: effects of chain length and type on the efficiencies of macrocyclic ring forming photoreactions of tethered α-silyl ether phthalimide substrates. J. Am. Chem. Soc. 130, 2276–2284 (2008)CrossRefGoogle Scholar
  19. 19.
    D.W. Cho, C. Quan, H.J. Park, J.H. Choi, S.R. Kim, T.G. Hyung, U.C. Yoon, S.H. Kim, Y.X. Jin, P.S. Mariano, Studies aimed at elucidating factors involved in the control of chemoselectivity in single electron transfer promoted photoreactions of branched-polydonor substituted phthalimides. Tetrahedron 66, 3173–3186 (2010)CrossRefGoogle Scholar
  20. 20.
    T. Maruyama, Y. Mizuno, I. Shimizu, S. Suga, J. Yoshida, Reactions of N-acyliminium ion pool with benzylsilanes. Inspection of a radical/cation/radical cation chain mechanism involving oxidative c-si bond cleavage. J. Am. Chem. Soc. 129, 1902–1903 (2007)CrossRefGoogle Scholar
  21. 21.
    Y. Kanaoka, Photoreactions of cyclic imides. Examples of synthetic organic photochemistry. Acc. Chem. Res. 11, 407–413 (1978)CrossRefGoogle Scholar
  22. 22.
    J.D. Coyle, Phthalimide and its derivatives, in Synthetic organic photochemistry, ed. by W.M. Horspool (Plenum Press, New York, 1984), pp. 259–284CrossRefGoogle Scholar
  23. 23.
    Y. Sato, H. Nakai, H. Ogiwara, T. Mizoguchi, Y. Migita, Y. Kanaoka, Photochemistry of the phthalimide system. V. Photocyclization of phthalimides with sulfide chain: synthesis of azo-cyclols by δ-, ε- and ζ-hydrogen abstraction. Tetrahedron Lett. 14, 4565–4568 (1973)CrossRefGoogle Scholar
  24. 24.
    M. Machida, M. Nakamura, K. Oda, H. Takechi, K. Ohno, H. Nakai, Y. Sato, Y. Kanaoka, Photochemistry of the phthalimide system. 40. Photoreaction of phthalimides possessing an ortho-methylphenyl group in their N-side chain. Synthesis of tetracyclic nitrogen heterocycles. Heterocycles 26, 2683–2690 (1987)CrossRefGoogle Scholar
  25. 25.
    J.O. Howell, J.M. Concalves, C. Amatore, L. Klasinc, R.M. Wightman, J.K. Kochi, Electron transfer from aromatic hydrocarbons and their π-complexes with metals. Comparison of the standard oxidation potentials and vertical ionization potentials. J. Am. Chem. Soc. 106, 3968–3976 (1984)CrossRefGoogle Scholar

Copyright information

© Springer Science+Business Media B.V. 2011

Authors and Affiliations

  • Hea Jung Park
    • 1
  • Jung Hei Choi
    • 1
  • Byeol Na Park
    • 1
  • Ung Chan Yoon
    • 1
  • Dae Won Cho
    • 2
  • Patrick S. Mariano
    • 3
  1. 1.Department of Chemistry, and Chemistry Institute for Functional MaterialsPusan National UniversityBusanKorea
  2. 2.Department of ChemistryYeungnam UniversityGyeongsan, GyeongbukKorea
  3. 3.Department of Chemistry and Chemical BiologyUniversity of New MexicoAlbuquerqueUSA

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