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Beiträge zur Chemie der Pyrrolpigmente, 25. Mitt. Die diastereomeren (geometrisch isomeren) Biliverdindimethylester—Struktur, Konfiguration und Konformation

On the chemistry of pyrrole pigments, XXV.: The diastereomeric (geometrically isomeric) biliverdindimethylesters—Structure, configuration and conformation

  • Organische Chemie und Biochemie
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Abstract

Photoisomerization of the symmetrically substituted bilatrienes-abc1 and2 adsorbed on aluminum oxide yields the photoisomers1′ and2′, whereas the biliverdindimethylester (3) gives rise to two isomers3′ and3″. By X-ray photoelectron spectrometry of the N1s-level all these diastereomers were shown to have a bislactam structure. From1H-NMR experiments (chemical shifts, Lanthanide induced shifts, double resonance experiments) the configurations (Z,Z,Z) at the methin positions were assigned to the educts—the photoisomers1′ and2′ having the configurations (Z,Z,E). The configurations (Z,Z,E) and (E,Z,Z) could be assigned to the diastereomers3′ and3″. The conformational aspects within these series are discussed and on the basis of several studies asyn-syn-syn-helical arrangement is deduced for the systems of configuration (Z,Z,Z). For the (Z,Z,E) isomers in the region of (Z)-configuration a conformation resembling the (Z,Z,Z)-systems is reasonable, but in the region of configuration (E) a stronger twisting at the methin single bond due to steric crowding should be favoured.

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Authors and Affiliations

  1. Institut für Organische Chemie, Universität Wien, A-1090, Wien, Österreich

    Heinz Falk, Karl Grubmayr, Ernst Haslinger, Thomas Schlederer & Klaus Thirring

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  1. Heinz Falk
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  2. Karl Grubmayr
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  3. Ernst Haslinger
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  4. Thomas Schlederer
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  5. Klaus Thirring
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Additional information

24. Mitt.:H. Falk undG. Höllbacher, Mh. Chem.109, 1429 (1978).

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Falk, H., Grubmayr, K., Haslinger, E. et al. Beiträge zur Chemie der Pyrrolpigmente, 25. Mitt. Die diastereomeren (geometrisch isomeren) Biliverdindimethylester—Struktur, Konfiguration und Konformation. Monatshefte für Chemie 109, 1451–1473 (1978). https://doi.org/10.1007/BF00906057

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  • DOI: https://doi.org/10.1007/BF00906057

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