Photosynthesis Research

, Volume 111, Issue 1–2, pp 1–8 | Cite as

Synthesis of oligomethylene-strapped chlorophyll derivatives and optical properties of their stereoisomers in a solution

  • Hitoshi Tamiaki
  • Hiroshi Takebe
  • Shin-ichi Sasaki
  • Yumiko Kataoka
Regular Paper


Methyl pheophorbide-a/a′ derivatives covalently linked with oligomethylene chains at the 3-CH2OCO– and 132-COO– moieties in a molecule were prepared by modifying chlorophyll-a through intramolecular ring-closing metathesis of vinyl groups. At least, a C10-length between the 33- and 134-positions was necessary for the cyclization and connection of a C12-strap was the most suitable to achieve the highest closure yield. The oligomethylene chain in 132 R-epimers derived from methyl pheophorbide-a covered the α-face of the chlorin π-plane and the strap in the corresponding 132 S-epimers protected the β-face. Synthetic 132 R-epimer with a dodecamethylene chain gave a flat chlorin π-plane, while the decamethylene chain in the 132 R-epimer distorted the π-system due to its shorter linkage. The distortion by strapping in the 132 R-epimer induced a slight blue-shift of Qy peak in dichloromethane. CD spectra of the 132 R-epimers were similarly dependent on the chain length, i.e., the distortion of π-plane. Visible absorption and CD spectra of all the strapped 132 S-epimers were almost identical and only slightly different from those of the unstrapped. The strapping in the 132 S-epimers shifted the Qy peak bathochromically.


Circular dichroism spectra π-plane distortion Pheophorbide Ring-closing metathesis Site energy Visible absorption spectra 



Circular dichroism


Catalytic hydrogenation


2-Chloro-1-methylpyridinium iodide




1-Ethyl-3-[3-(N,N-dimethylamino)propyl]carbodiimide (water-soluble carbodiimide)


Flash column chromatography


High performance liquid chromatography


Nuclear magnetic resonance


Ring-closing metathesis





We thank Dr. Yasuhiko Kureishi for assistance in molecular modeling calculation. This work was partially supported by a Grant-in-Aid for Scientific Research (A) (No. 22245030) (to HT) from the Japan Society for the Promotion of Science (JSPS) and for Young Scientists (B) (No. 21750154) (to SS) from the Ministry of Education, Culture, Sports, Science and Technology (MEXT) of the Japanese Government.

Supplementary material

11120_2010_9616_MOESM1_ESM.doc (1.3 mb)
The online version of this article (doi: 10.1007/s11120-) contains supplementary material, which is available to authorized users (DOC 1377 kb)


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Copyright information

© Springer Science+Business Media B.V. 2011

Authors and Affiliations

  • Hitoshi Tamiaki
    • 1
  • Hiroshi Takebe
    • 1
  • Shin-ichi Sasaki
    • 1
    • 2
  • Yumiko Kataoka
    • 1
  1. 1.Department of Bioscience and Biotechnology, Faculty of Science and EngineeringRitsumeikan UniversityKusatsuJapan
  2. 2.Nagahama Institute of Bio-Science and TechnologyNagahamaJapan

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