C132-Methylation of methyl pheophorbide a and stereoselective preparation of methyl (132R)-methylpyropheophorbide a

Abstract

The (132R)-methoxycarbonyl group of methyl pheophorbide a, one of the chlorophyll-a derivatives, was converted to a methyl group through methylation at the C132 position followed by removal of the methoxycarbonyl group. The methylation of the C132 carboanion gave a 4:1 mixture of methyl 132-methyl-pheophorbide a and its 132-epimer. The successive pyrolysis of the major methylated product afforded methyl (132R)-methyl-pyropheophorbide a with a small amount of its (132S)-epimer. The substitution effects at the C132 position including stereochemistry were discussed on the basis of 1D/2D NMR, UV–vis absorption, and circular dichroism spectroscopic analyses as well as molecular modeling simulation.