Bulletin of the Korean Chemical Society

Korean Chemical Society (대한화학회)
권호 표지
DOI QR코드

DOI QR Code

Photocyclization Reactions of N-(Trimethylsilylmethoxyalkyl)Phthalimides. Efficient and Regioselective Route to Heterocycles

  • Yoon Ung Chan (Department of Chemistry, Pusan National University) ;
  • Oh Ju Hee (Department of Chemistry, Pusan National University) ;
  • Lee, Sang Jin (Department of Chemistry, Pusan National University) ;
  • Kim, Dong Uk (Department of Chemistry, Pusan National University) ;
  • Lee, Jong Gun (Department of Chemistry, Pusan National University) ;
  • Kang Kyung-Tae (Department of Chemical Education, Pusan National University) ;
  • Mariano Patrick S. (Department of Chemistry, University of Maryland)
  • Published : 1992.04.20
Download PDF
⟨ Previous Next ⟩

Abstract

Studies have been conducted to explore single electron transfer (SET) induced photocyclization reactions of N-(trimethylsilylmethoxyalkyl)phthalimides(alkyl=E thyl, n-propyl, n-butyl, n-pentyl, and n-octyl). Photocyclizations occur in methanol in high yields to produce cyclized products in which phthalimide carbonyl carbon is bonded to the carbon of side chain in place of the trimethylsilyl group. Mechanism for these photocyclizations involving intramolecular SET from oxygen in the $\alpha-silylmethoxy$ groups to the singlet excited state phthalimide moieties followed by desilylation of the intermediate $\alpha-silylmethoxy$ cation radicals and cyclization by radical coupling are proposed. In contrast, photoreaction of N-(trimethylsilylmethoxyethyl) phthalimide in acetone follows different reaction routes to produce two cyclized products in which carbon-carbon bond formation takes place between the phthalimide carbonyl carbon and the carbon $\alpha$ to silicon and oxygen atoms via triplet carbonyl hydrogen abstraction triplet carbonyl silyl group abstraction pathways. The normal singlet SET pathway dominates these triplet processes for photoreaction of this substance in methanol. The efficient and regioselective cyclization reactions observed for photolysis in methanol represent synthetically useful processes for construction of medium and large ring heterocyclic compounds.

Keywords

References

  1. J. Am. Chem. Soc. v.106 M. A. Brumfield;S. L. Quillen;U. C. Yoon;P. S. Mariano
  2. J. Org. Chem. v.53 M. A. Brumfield;U. C. Yoon;E. Hasegawa;P. S. Mariano
  3. J. Am. Chem. Soc. v.109 U. C. Yoon;J. U. Kim;E. Hasegawa;P. S. Mariano
  4. J. Am. Chem. Soc. v.110 E. Hasegawa;W. Xu;P. S. Mariano;U. C. Yoon;J. U. Kim
  5. Heterocycles v.29 U. C. Yoon;H. J. Kim;P. S. Mariano
  6. Acc. Chem. Res. v.11 Y. Kanaoka
  7. Synthetic Organic Photochemistry J. D. Coyle;W. M. Horspool(ed.)
  8. Organic Photochemistry v.5 P. H. Mazzocchi;A. Padwa(ed.)
  9. J. Phys. Chem. v.76 E. Heyon;T. Ibata;N. N. Lichtin;M. Simic
  10. Chem. Lett. Y. Yoshida;S. Isoc
  11. Tetrahedron Lett. v.14 Y. Kanaoka;Y. Migita;K. Koyama;Y. Sato;H. Nakai;T. Mizoguchi
  12. Silicon in Organic Synthesis E. Colvin
  13. Tetrahedron Lett. Y. Kanaoka;Y. Migita;Y. Sato;H. Nakai
  14. Heterocycles v.2 H. Nakai;Y. Sato;H. Ogiwara;T. Mizoguchi;Y. Kanaoka
  15. Tetrahedron Lett. Y. Kanaoka;Y. Migita
  16. U. C. Yoon;Y. C. Kim;J. J. Choi;D. U. kim;P. S. Mariano;I. S. Cho;Y. T. Jeon
  17. Ph. D. Thesis, University of Maryland M. A. Brumfield
  18. Tetrahedron Lett. v.28 Y. Yoshida;S. Isoe

Cited by

  1. ChemInform Abstract: Photocyclization Reactions of N-(Trimethylsilylmethoxyalkyl) phthalimides. Efficient and Regioselective Route to Heterocycles. vol.23, pp.35, 1992, https://doi.org/10.1002/chin.199235088
  2. Synthesis of Medium- and Large-Ring Compounds Initiated by Photochemical Decarboxylation of ω-Phthalimidoalkanoates vol.80, pp.3, 1992, https://doi.org/10.1002/hlca.19970800324
  3. Photoaddition Reactions of Silyl Ketene Acetals with Aromatic Carbonyl Compounds: A New Procedure for β-Hydroxyester Synthesis vol.23, pp.9, 2002, https://doi.org/10.5012/bkcs.2002.23.9.1218
  4. The Synthetic Potential of SET Photochemistry of Silicon-Substituted Polydonor-Linked Phthalimides vol.27, pp.8, 1992, https://doi.org/10.5012/bkcs.2006.27.8.1099
  5. N-Alkylation of imides using phase transfer catalysts under solvent-free conditions vol.45, pp.5, 1992, https://doi.org/10.1002/jhet.5570450519
  6. Studies aimed at elucidating factors involved in the control of chemoselectivity in single electron transfer promoted photoreactions of branched-polydonor substituted phthalimides vol.66, pp.17, 2010, https://doi.org/10.1016/j.tet.2010.02.074
  7. Studies of Silyl-Transfer Photochemical Reactions of N-[(Trimethylsilyl)alkyl]saccharins vol.31, pp.9, 1992, https://doi.org/10.5012/bkcs.2010.31.9.2453
  8. Synthesis, structure, spectroscopic investigations, and computational studies of optically pure β-ketoamide vol.61, pp.7, 2016, https://doi.org/10.1134/s1063774516070075