1,3-Dipolar Cycloaddition of Methyl Pheophorbide-a andSyn-thesis of Chlorophyll Derivative

Abstract

From methyl pheophorbide-a (MPa, 1), the pheophorbide-a derivative substituted with hydro-pyrazol 2 was obtained by the 1,3-dipolar cycloaddition of vinyl group at 3-position with diazomethane. Ring opening of this chlorin was performed by heating to rearrange the hydropyrzaol ring into the cyclopropyl group. In basic condition the cyclopropyl-substituted chlorin 3 was converted into pyropheophorbide 4 by demethoxyformylation. The diazoethane was chosen as another dipole and reacted with chlorin 1 in 1,3-dipolar cycloaddition style to give 2-methylcyclopropyl-substituted stereoisomer chlorin 5. The treatment for demethoxyformylation like chlorin 2 yielded pyropheophorbide 6. The structures of all new chlorophyll-a deriva-tives 2～6 were characterized by elemental analysis, UV, IR and ¹H NMR spectra.

Key words: pheophorbide, chlorophyll-a, pyropheophorbide, photodynamic therapy, 1,3-dipolar cycloaddition

Cite this article

JI Jian-Ye^a,LI Jia-Zhu^b,WANG Hu^b,LI Fu-Guo^b,HAN Guang-Fan^c
SHIM Young Key^d,WANG Jin-Jun*^,b. 1,3-Dipolar Cycloaddition of Methyl Pheophorbide-a andSyn-thesis of Chlorophyll Derivative[J]. Chin. J. Org. Chem., 2006, 26(12): 1714-1719.

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