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Oxidative ring-openings of octaethyl-2-oxochlorin: Regioisomeric β-oxobiliverdins

Ruoshi Li

Department of Chemistry, University of Connecticut, Storrs, CT 06369-3060, USA

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Matthias Zeller

Department of Chemistry, Purdue University, 560 Oval Drive, West Lafayette, IN 47907-2084, USA

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, and

Christian Brückner

Department of Chemistry, University of Connecticut, Storrs, CT 06369-3060, USA

E-mail Address: c.bruckner@uconn.edu

Corresponding author, tel.: +1-860-486-2743, fax: +1-860-486-2981

SPP full member in good standing

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https://doi.org/10.1142/S1088424618500608Cited by:2 (Source: Crossref)

Abstract

We describe the oxidative ring opening of octaethyl-2-oxochlorin using two different oxidation methods, both providing a mixture of all possible regioisomeric products (8- $α$ through 8- $δ)$ . While isomers 8- $α$ , 8- $γ$ , and 8- $δ$ formed in isolable yields and relative ratios that varied with the oxidation method used, isomer 8- $β$ was invariably formed in trace amounts only. The three major products were spectroscopically characterized (IR, MS, 1D- and 2D NMR spectroscopy) and their configurations were deduced by NMR spectroscopy. The spectroscopic findings correlated well with the single crystal X-ray structure of the novel cleavage product 8- $α$ and the known compound of 8- $γ$ . The work broadens the number of octaethylporphyrin-derived biliverdin derivatives available and presents a methodology of controlling the biliverdin backbone configuration by introduction of a $β$ -ketone functionality into select positions.

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