MECHANISM OF PHOTOOXYGENATION OF THE CD (II) COMPLEX OF PYROPHEOPHORBIDE A METHYL ESTER

Photooxygenation of (pyropheophorbidato a methyl ester)cadmium (II) was studied using ^18,18O₂ labeling of the molecular oxygen required for cleavage of the macrocycle. After reductive demetallation of the primary oxidation product (4,5-dioxo-4,5-secopyropheophorbidato a methyl ester)cadmium (II), the isotope content of formylbilinone 4a was analyzed by repeated-scan fast atom bombardment mass spectrometry. Comparison of the spectroscopic data of the labeled pigment 4a with the statistical probabilities of¹⁸ O isotope incorporation calculated for four possible reaction mechanisms clearly proves that photooxidative ring cleavage occurred by the one-molecule mechanism, i.e. the terminal oxygen atoms of 4a were derived from one oxygen molecule. Furthermore, a study of the exchange of the¹⁸ O-labeled atoms revealed that no exchange occurs within the pH 4.5–9.5 range. In stronger alkaline or acidic solutions, only the oxygen atom of the formyl group is exchanged. Hydrolysis of the methyl ester group of 4a was achieved, without loss of the¹⁸ O label on the formyl group, at pH 7.2 in the presence of pig liver esterase.