Chinese Journal of Organic Chemistry >
Alkynylation of Pyropheophorbide-a and Synthesis of Chylorophyllous Chlorin Derivatives
Received date: 2012-05-02
Revised date: 2012-05-29
Online published: 2012-06-05
Supported by
Project supported by the National Natural Science Foundations of China (No. 20972036) and the Natural Science Foundation of Shandong Province of China (No. Y2008B49).
Methyl pyropheophorbide-a was used as starting material and converted into 3-formyl or 3-acetyl substituted and E-ring protected reactive precursors. The Grignard reactions of these carbonyl groups introduced alkynyl groups at 3-position to build the tert-alcohol or sec-alcohol structures. Further dehydrations and oxidations produced terminal eneyne and ketyne substituted chlorins, respectively. The pyropheophorbide-a with long chain alkyl group at 3-position was obtained by Grignard reaction with decyl magnesium bromide, protection for E-ring and oxidation of C(3)-hydroxyl group from 3-formylpyropheo- phorbide-a, converted into chlorin containing eneyne moiety in chain by acid-catalyzed dehydration. The structures of all new chlorin derivatives were characterized by elemental analysis, UV, IR and 1H NMR spectra. The possible mechanisms about corresponding reactions were tentatively proposed.
Key words： chlorophyll-a; pyropheophorbide; chlorin; alkynylation; chemical modification
Yin Jungang , Wang Zen , Yang Ze , Jin Yingxue , Wang Jinjun . Alkynylation of Pyropheophorbide-a and Synthesis of Chylorophyllous Chlorin Derivatives[J]. Chinese Journal of Organic Chemistry, 2012 , 32(10) : 1936 -1943 . DOI: 10.6023/cjoc201205002
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