Amino Acids

, Volume 42, Issue 6, pp 2275–2282 | Cite as

Photorelease of amino acids from novel thioxobenzo[f]benzopyran ester conjugates

  • Ana M. Piloto
  • Ana M. S. Soares
  • Susana P. G. Costa
  • M. Sameiro T. Gonçalves
Original Article

Abstract

Aiming at the enhancement of the performance of (9-methoxy-3-oxo-3H-benzo[f]benzopyran-1-yl) methyl ester as photocleavable protecting group for the carboxylic acid function at long-wavelengths, 9-methoxy-3-thioxo-3H-benzo[f]benzopyran-l-valine and l-phenylalanine model conjugates were prepared through a thionation reaction of the corresponding oxo-benzobenzopyrans. These thioxobenzobenzopyran derivatives were subjected to photocleavage reactions in the same conditions as the parent oxo-benzobenzopyrans at different wavelengths of irradiation, and photocleavage data were obtained. It was found that the exchange of the carbonyl by a thiocarbonyl group enhanced the performance of the heterocyclic protecting group at 419 nm by improving the photolysis rates, making it an appropriate group for practical applications at long wavelengths.

Keywords

Thioxobenzobenzopyran Benzocoumarin Amino acids Photolabile protecting groups 

Notes

Acknowledgments

Thanks are due to the Foundation for Science and Technology (Portugal) for financial support through project PTDC/QUI/69607/2006 (FCOMP-01-0124-FEDER-007449), and a PhD grant to A.M.P. (SFRH/BD/61459/2009). The NMR spectrometer Bruker Avance III 400 is part of the National NMR Network and was purchased in the framework of the National Program for Scientific Re-equipment, contract REDE/1517/RMN/2005 with funds from POCI 2010 (FEDER) and FCT.

References

  1. Abelson J, Simon M, Marriott G (1998) Caged compounds. Academic Press, New YorkGoogle Scholar
  2. Bochet CG (2000) Wavelength-selective cleavage of photolabile protecting groups. Tetrahedron Lett 41:6341–6346CrossRefGoogle Scholar
  3. Bochet CG (2002) Photolabile protecting groups and linkers. J Chem Soc Perkin Trans 1:125–142Google Scholar
  4. Dinkel C, Schultz C (2003) Synthesis of caged myo-inositol 1, 3, 4, 5-tetrakisphosphate. Tetrahedron Lett 44:1157–1159CrossRefGoogle Scholar
  5. Dinkel C, Wichmann O, Schultz C (2003) Versatile reagents to introduce caged phosphates. Tetrahedron Lett 44:1153–1155CrossRefGoogle Scholar
  6. Fernandes MJG, Gonçalves MST, Costa SPG (2007) Photorelease of amino acid neurotransmitters from pyrenylmethyl ester conjugates. Tetrahedron 63:10133–10139CrossRefGoogle Scholar
  7. Fernandes MJG, Gonçalves MST, Costa SPG (2008a) Comparative study of polyaromatic and polyheteroaromatic fluorescent photocleavable protecting groups. Tetrahedron 64:3032–3038CrossRefGoogle Scholar
  8. Fernandes MJG, Gonçalves MST, Costa SPG (2008b) Neurotransmitter amino acid-oxobenzo[f]benzopyran conjugates: synthesis and photorelease studies. Tetrahedron 64:11175–11179CrossRefGoogle Scholar
  9. Fonseca ASC, Gonçalves MST, Costa SPG (2007) Photocleavage studies of fluorescent amino acid conjugates bearing different types of linkages. Tetrahedron 63:1353–1359CrossRefGoogle Scholar
  10. Fonseca ASC, Gonçalves MST, Costa SPG (2010) Light-induced cleavage of phenylalanine model conjugates based on coumarins and quinolones. Amino Acids 39:699–712PubMedCrossRefGoogle Scholar
  11. Givens RS, Weber JFW, Conrad PG, Orosz G, Donahue SL, Thayer SA (2000) New phototriggers 9: p-hydroxyphenacyl as a C-terminus photoremovable protecting group for oligopeptides. J Am Chem Soc 122:2687–2697CrossRefGoogle Scholar
  12. Greene TW, Wuts GM (1999) Protective groups in organic chemistry, 3rd edn. John Wiley, New YorkCrossRefGoogle Scholar
  13. Grewer C, Jager J, Carpenter BK, Hess GP (2000) A new photolabile precursor of glycine with improved properties: a tool for chemical kinetic investigations of the glycine receptor. Biochemistry 39:2063–2070PubMedCrossRefGoogle Scholar
  14. Isidro-Llobet A, Alvarez M, Albericio F (2009) Amino acid-protecting groups. Chem Rev 109:2455–2504PubMedCrossRefGoogle Scholar
  15. Jana A, Atta S, Sarkar SK, Singh NDP (2010) 1-Acetylpyrene with dual functions as an environment-sensitive fluorophore and fluorescent photoremovable protecting group. Tetrahedron 66:9798–9807CrossRefGoogle Scholar
  16. Jesberger M, Davis TP, Barner L (2003) Applications of Lawesson’s reagent in organic and organometallic syntheses. Synthesis 13:1929–1958CrossRefGoogle Scholar
  17. Li YM, Shi J, Caia R, Chen XY, Guo QX, Liu L (2010a) Development of new quinoline-based photo-labile groups for photo-regulation of bioactive molecules. Tetrahedron Lett 51:1609–1612CrossRefGoogle Scholar
  18. Li YM, Shi J, Caia R, Chen XY, Luo ZF, Guo QX (2010b) New quinoline-based caging groups synthesized for photo-regulation of aptamer activity. J Photochem Photobiol A Chem 211:129–134CrossRefGoogle Scholar
  19. Loudwig S, Goeldner M (2001) N-Methyl-N-(o-nitrophenyl)carbamates as photolabile alcohol protecting groups. Tetrahedron Lett 42:7957–7959CrossRefGoogle Scholar
  20. Ma C, Steinmetz MG, Kopatz EJ, Rathore R (2005) Photochemical cleavage and release of carboxylic acids from α-keto amides. J Org Chem 70:4431–4442PubMedCrossRefGoogle Scholar
  21. Mayer G, Heckel A (2006) Biologically active molecules with a “light switch”. Angew Chem Int Ed 45:4900–4921CrossRefGoogle Scholar
  22. Morris JV, Mahaney MA, Huber JR (1976) Fluorescence quantum yield determinations. 9, 10-Diphenylanthracene as a reference standard in different solvents. J Phys Chem 80:969–974CrossRefGoogle Scholar
  23. Muller C, Even P, Viriot M-L, Carré M-C (2001) Protection and labeling of thymidine by a fluorescent photolabile group. Helv Chim Acta 84:3735–3741CrossRefGoogle Scholar
  24. Papageorgiou G, Ogden DC, Barth A, Corrie JET (1999) Photorelease of carboxylic acids from 1-acyl-7-nitroindolines in aqueous solution: a reagent for rapid and efficient photorelease of L-glutamate. J Am Chem Soc 121:6503–6504CrossRefGoogle Scholar
  25. Pelliccioli AP, Wirz J (2002) Photoremovable protecting groups: reaction mechanisms and applications. Photochem Photobiol Sci 1:441–458PubMedCrossRefGoogle Scholar
  26. Peng L, Wirz J, Goeldner M (1997) 2-Nitrobenzyl quaternary ammonium derivatives photoreleasing nor-butyrylcholine in the microsecond time range. Tetrahedron Lett 38:2961–2964CrossRefGoogle Scholar
  27. Pillai VNR (1980) Photoremovable protecting groups in organic synthesis. Synthesis 9:1–26Google Scholar
  28. Piloto AM, Rovira D, Costa SPG, Gonçalves MST (2006) Oxobenzo[f]benzopyrans as new fluorescent photolabile protecting groups for the carboxylic function. Tetrahedron 62:11955–11962CrossRefGoogle Scholar
  29. Schaper K, Mobarekah SAM, Grewer C (2002) Synthesis and photophysical characterization of a new, highly hydrophilic caging group. Eur J Org Chem 2002:1037–1046Google Scholar
  30. Singh AK, Khade PK (2005a) 3-Nitro-2-naphthalenemethanol: a photocleavable protecting group for carboxylic acids. Tetrahedron 61:10007–10012CrossRefGoogle Scholar
  31. Singh AK, Khade PK (2005b) Anthracene-9-methanol—a novel fluorescent phototrigger for biomolecular caging. Tetrahedron Lett 46:5563–5566CrossRefGoogle Scholar
  32. Soares AMS, Costa SPG, Gonçalves MST (2010a) Oxazole light triggered protecting groups: synthesis and photolysis of fused heteroaromatic conjugates. Tetrahedron 66:8189–8195CrossRefGoogle Scholar
  33. Soares AMS, Costa SPG, Gonçalves MST (2010b) 2-Oxo-2H-benzo[h]benzopyran as a new light sensitive protecting group for neurotransmitter amino acids. Amino Acids 39:121–133PubMedCrossRefGoogle Scholar
  34. Wang P, Hu H, Wang Y (2007) Novel photolabile protecting group for carbonyl compounds. Org Lett 9:1533–1535PubMedCrossRefGoogle Scholar
  35. Yu J-Y, Tang W-J, Wang H-B, Song Q-H (2007) Anthraquinon-2-ylethyl-1’, 2’-diol (Aqe-diol) as a new photolabile protecting group for aldehydes and ketones. J Photochem Photobiol A Chem 185:101–105CrossRefGoogle Scholar

Copyright information

© Springer-Verlag 2011

Authors and Affiliations

  • Ana M. Piloto
    • 1
  • Ana M. S. Soares
    • 1
  • Susana P. G. Costa
    • 1
  • M. Sameiro T. Gonçalves
    • 1
  1. 1.Centro de QuímicaUniversidade do MinhoBragaPortugal

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