Summary
In preparations of biliverdin-IXα-dimethyl ester (2 b) from bilirubin-IXα (1) the ratio of the XIIIα- and IIIα-isomers3 b and4 b, formed via intermolecular scrambling, should be unity. However, irrespective of the synthetic variant considered, the amount of4 b obtained usually is exceptionally low. This is partly ascribed to a consecutive reaction of4 b in acidic methanol affording the chiral diastereomeric bridged biliverdins5 (a undb) and6 (a andb), respectively.
Zusammenfassung
Bei der Darstellung von Biliverdin-IXα-dimethylester (2 b) aus Bilirubin-IXα (1) sollte das Verhältnis der durch intermolekulares Scrambling gebildeten XIIIα- und IIIα-Isomeren3 b bzw.4 b eins betragen. Tatsächlich aber ist die Ausbeute an4 b, unabhängig von der verwendeten synthetischen Variante, immer sehr klein. Dieser Umstand läßt sich zumindest teilweise auf eine spezifische Reaktion von4 b in saurem Methanol zurückführen, in deren Verlauf die chiralen diastereoisomeren überbrückten Biliverdine5 (a undb) sowie6 (a undb) gebildet werden.
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References and notes
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Krois D., Lehner H. (unpublished observations)
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Krois, D., Lehner, H. On the fate of biliverdin-IIIα-dimethyl ester formed by scrambling during syntheses of biliverdin-IXα-dimethyl ester from bilirubin. Monatsh Chem 120, 575–580 (1989). https://doi.org/10.1007/BF00810844
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DOI: https://doi.org/10.1007/BF00810844