Chlorophyll synthetase cannot synthesize chlorophyll a′

Abstract
Chlorophyll synthetase catalyzes the last step of chlorophyll biosynthesis, namely prenylation (esterification) of chlorophyllide with phytyl diphosphate or geranylgeranyl diphosphate. During investigation of various chlorophyllide derivatives as potential substrates we observed lower esterification with increasing percentages of chlorophyllide a′ in epimeric mixtures of chlorophyllides a and a′. To avoid epimerization during esterification, we studied the reaction in detail with model compounds [zinc‐132(R)‐methoxy‐pheophorbide a and zinc‐132(S)‐methoxy‐pheophorbide a, zinc‐132(R)‐methoxy‐pyropheophorbide a and zinc‐chlorin e6‐131, 152‐dimethylester]. We conclude that compounds which have the 132‐carbomethoxy group at the same side of the macrocycle as the propionic side chain of ring D are neither substrates nor competitive inhibitors. Only compounds having the 132‐carbomethoxy group at the opposite site are substrates for the enzyme. Naturally occuring chlorophyll a′ must be formed by epimerization after esterification.

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