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

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-[Formula: see text] through 8-[Formula: see text]. While isomers 8-[Formula: see text], 8-[Formula: see text], and 8-[Formula: see text] formed in isolable yields and relative ratios that varied with the oxidation method used, isomer 8-[Formula: see text] 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-[Formula: see text] and the known compound of 8-[Formula: see text]. 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 [Formula: see text]-ketone functionality into select positions.