Stepwise Reduction of Octaethyl-β,β'-dioxochlorin Isomers: Access to Structurally and Electronically Diverse...

Di- and tetrahydroporphyrins (chlorins, bacteriochlorins and isobacteriochlorins, respectively) are key "pigments of life." They have been a major focus of attention in synthetic tetrapyrrole chemistry. A long-known one-pot epoxidation/epoxide ring-opening/pinacol-pinacolone rearrangement of octaethylporphyrin (OEP) generates a β-ketochlorin and all five β,β'-diketone isomers. We present herein the single and double reductions of all isomers of the β,β'-diketones, generating hydroxychlorin and β-hydroxy-β-ketodihydroporphyrin isomers, generally in regioselective manner, and sets of separable stereoisomeric dihydroxytetrahydroporphyrin regioisomers. The connectivity of the regio- and stereoisomers were determined spectroscopically and, in many cases, using single-crystal X-ray crystallography. The optical properties of the chlorin-, bacteriochlorin-, and isobacteriochlorin-type chromophores are described. They highlight general observations on the regiochemical effects of the β-oxo-auxochrome. This contribution thus delineates the formation of a range of regio- and stereoisomers of a family of chromophores with broadly varying optical properties from a single and readily available starting material (OEP) in two straightforward steps, albeit requiring extensive chromatography.