Intramolecular Sensitization of Photocleavage of the Photolabile 2-(2-Nitrophenyl)propoxycarbonyl (NPPOC) Protecting Group: Photoproducts and Photokinetics of the Release of Nucleosides

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Woell_Chem_Eur_J_2008.pdf
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2008
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Smirnova, Julia
Prykota, Tamara
Bühler, Jochen
Stengele, Klaus-Peter
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Chemistry. 2008, 14(21), pp. 6490-6497. ISSN 0947-6539. eISSN 0947-6539. Available under: doi: 10.1002/chem.200800613
Zusammenfassung

Novel photolabile protecting groups based on the 2-(2-nitrophenyl)propoxycarbonyl (NPPOC) group with a covalently linked thioxanthone as an intramolecular triplet sensitizer exhibit significantly enhanced light sensitivity under continuous illumination. Herein we present a detailed study of the photokinetics and photoproducts of nucleosides caged with these new protecting groups. Relative to the parent NPPOC group, the light sensitivity of the new photolabile protecting groups is enhanced by up to a factor of 21 at 366 nm and is still quite high at 405 nm, the wavelength at which the sensitivity of the parent compound is practically zero. A new pathway for deprotection of the NPPOC group proceeding through a nitroso benzylalcohol intermediate has been discovered to complement the main mechanism, which involves elimination. Under standard conditions of lithographic DNA-chip synthesis, some of the new compounds, while maintaining the same chip quality, react ten times faster than the unmodified NPPOC-protected nucleosides.

Zusammenfassung in einer weiteren Sprache
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540 Chemie
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DNA chips, energy transfer, photochemistry, protecting groups, sensitization
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ISO 690WÖLL, Dominik, Julia SMIRNOVA, Marina GALETSKAYA, Tamara PRYKOTA, Jochen BÜHLER, Klaus-Peter STENGELE, Wolfgang PFLEIDERER, Ulrich STEINER, 2008. Intramolecular Sensitization of Photocleavage of the Photolabile 2-(2-Nitrophenyl)propoxycarbonyl (NPPOC) Protecting Group: Photoproducts and Photokinetics of the Release of Nucleosides. In: Chemistry. 2008, 14(21), pp. 6490-6497. ISSN 0947-6539. eISSN 0947-6539. Available under: doi: 10.1002/chem.200800613
BibTex
@article{Woll2008Intra-9683,
  year={2008},
  doi={10.1002/chem.200800613},
  title={Intramolecular Sensitization of Photocleavage of the Photolabile 2-(2-Nitrophenyl)propoxycarbonyl (NPPOC) Protecting Group: Photoproducts and Photokinetics of the Release of Nucleosides},
  number={21},
  volume={14},
  issn={0947-6539},
  journal={Chemistry},
  pages={6490--6497},
  author={Wöll, Dominik and Smirnova, Julia and Galetskaya, Marina and Prykota, Tamara and Bühler, Jochen and Stengele, Klaus-Peter and Pfleiderer, Wolfgang and Steiner, Ulrich}
}
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