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Synthesis of chlorophyll-c derivatives by modifying natural chlorophyll-a

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Abstract

Chlorophyll-a (Chl-a) was extracted from cyanobacterial cells and modified to methyl pyropheophorbide-a. The 3-vinyl-chlorin was transformed to zinc complex of the corresponding 3-acetyl-porphyrin. The zinc porphyrin was oxidized to give cis-7,8- and 17,18-dihydroxy-chlorins as well cis-7,8-cis-17,18-tetrahydroxybacteriochlorin. After zinc-demetallation, the isolated cis-7,8- and 17,18-diols were reduced at the 3-acetyl group and triply dehydrated under acidic conditions to afford two regioisomeric 3-vinyl-porphyrins, methyl divinyl-pyroprotopheophorbide-a possessing the 8-vinyl group and 17-propionate residue (one of the divinyl-protoChl-a derivatives) and methyl pyropheophorbide-c 1 possessing the 8-ethyl group and 17-acrylate residue (one of the Chl-c 1 derivatives), respectively. The resulting 7,8,17,18-tetrol was reduced and then acidically treated, giving five-fold dehydrated free base porphyrin, methyl pyropheophorbide-c 2 possessing the 3,8-divinyl groups and 17-acrylate residue (one of the Chl-c 2 derivatives). The visible absorption and fluorescence emission spectra of the three semi-synthetic 3-vinyl-porphyrins in dichloromethane were compared with those of the corresponding 8-ethyl-porphyrin bearing the 17-propionate residue, methyl pyroprotopheophorbide-a (one of the protoChl-a derivatives). The Soret and Qy absorption maxima were shifted to longer wavelengths with an increase of π-conjugation in a molecule: protoChl-a (8-CH2CH3/17-CH2CH2COOCH3) < divinyl-protoChl-a (8-CH=CH2/17-CH2CH2COOCH3) < Chl-c 1 (8-CH2CH3/17-CH=CHCOOCH3) < Chl-c 2 derivatives (8-CH=CH2/17-CH=CHCOOCH3). The 171,172-dehydrogenation broadened the absorption bands. The emission maxima were bathochromically shifted in the same order. The reaction mechanism of the present dehydration indicates that the biosynthetic pathway of Chls-c would include the hydroxylation of the 17-propionate reside at the 171-position and successive dehydration to the 17-acrylate residue.

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Scheme 1
Scheme 2
Fig. 1
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Abbreviations

APCI:

Atmospheric pressure chemical ionization

CD:

Circular dichroism

Chl:

Chlorophyll

DV:

Divinyl

FCC:

Flash column chromatography

HR:

High resolution

MS:

Mass spectra

ODS:

Octadecylated silica gel

PChl-a H :

Protochlorophyllide-a

pPhe:

Pyropheophorbide

pPPhe:

Pyroprotopheophorbide

pTSA:

p-Toluenesulfonic acid

RP:

Reversed-phase

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Acknowledgments

This work was partially supported by Grants-in-Aid for Scientific Research (A) (No. 22245030) as well as on Innovative Areas “Artificial Photosynthesis (AnApple)” (No. 24107002) from the Japan Society for the Promotion of Science (JSPS).

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Authors and Affiliations

  1. Graduate School of Life Sciences, Ritsumeikan University, Kusatsu, 525-8577, Shiga, Japan

    Meiyun Xu, Yusuke Kinoshita, Shogo Matsubara & Hitoshi Tamiaki

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  1. Meiyun Xu
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  2. Yusuke Kinoshita
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  3. Shogo Matsubara
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  4. Hitoshi Tamiaki
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Correspondence to Hitoshi Tamiaki.

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Xu, M., Kinoshita, Y., Matsubara, S. et al. Synthesis of chlorophyll-c derivatives by modifying natural chlorophyll-a . Photosynth Res 127, 335–345 (2016). https://doi.org/10.1007/s11120-015-0190-1

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