Total syntheses of sterically locked phycocyanobilin derivatives bearing a 15Z-anti or a 15E-anti CD-ring component

Total syntheses of sterically locked phycocyanobilin derivatives with a 15Z-anti or a 15E-anti CD-ring component were performed toward elucidation of the stereochemistry and function of the chromophore in phytochromes. In the course of the construction of a sterically locked 15E-anti CD-ring component employing 5-tosylpyrrolin-2-one derivatives as the D-ring, the Ts group was found to be rearranged under acidic conditions to give a mixture of regioisomers, both of which could be transformed into the same CD-ring precursor via detosylation with a base followed by Wittig-like coupling reaction. In addition, a sterically locked 15E-anti biliverdin derivative was also synthesized. Total syntheses of sterically locked phycocyanobilin derivatives bearing a 15Z-anti or a 15E-anti CD-ring component were performed towards elucidation of the stereochemistry and function of the chromophore in phytochromes.