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Zur Chemie der Pyrrolpigmente, 54. Mitt.: Phytochrommodellstudien: Ein 2,3-Dihydrobilatrien-abc-3-Cholesterylderivat

On the chemistry of pyrrole pigments, LIV.: Phytochrome model studies: A 2,3-dihydrobilatriene-abc-3-cholesteryl derivative

  • Organische Chemie Und Biochemie
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Monatshefte für Chemie - Chemical Monthly Aims and scope Submit manuscript

Abstract

The diastereomeric 2,3-Dihydrobilatrienes-abc derivatives (4Z, 9Z, 15Z)-7 and (4Z, 9Z, 15E)-7 bearing a cholesterylacetate moiety in position 3 of the chromophore are prepared. The reaction sequence contains an isomerisation step providing quantitative enantioselective formation of the chiral center in position 3. Configurations and conformations of the diastereomers are elucidated using1H- and13C-NMR spectra, NOE-difference spectra, 2D-NMR experiments (NOESY) and arguments from UV-VIS and CD data. It is concluded that the hydrophobic interactions between chromophore and cholesteryl-fragment yield a “compact” conformation where the two substructures are in close contact with each other. On the other hand these interactions seem to be too weak to induce significant changes in the chemistry, absorption spectra and conformational characterics of the bile pigment chromophore. Therefore hydrophobic interactions between chromophor and apolar amino acid residues of the protein in phytochrome should be of minor relevance for determining spectroscopic shifts.

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Authors and Affiliations

  1. Institut für Analytische, Organische und Physikalische Chemie, Johannes-Kepler-Universität Linz, A-4040, Linz, Austria

    Josef Edinger, Heinz Falk & Norbert Müller

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  1. Josef Edinger
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  2. Heinz Falk
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  3. Norbert Müller
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Edinger, J., Falk, H. & Müller, N. Zur Chemie der Pyrrolpigmente, 54. Mitt.: Phytochrommodellstudien: Ein 2,3-Dihydrobilatrien-abc-3-Cholesterylderivat. Monatsh Chem 115, 837–852 (1984). https://doi.org/10.1007/BF01120979

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  • DOI: https://doi.org/10.1007/BF01120979

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