Skip to main content
Journal of Wood Science

Official Journal of the Japan Wood Research Society

Download PDF
  • Note
  • Published:

Stereochemistry and biosynthesis of (+)-lyoniresinol, a syringyl tetrahydronaphthalene lignan in Lyonia ovalifolia var. elliptica I: isolation and stereochemistry of syringyl lignans and predicted precursors to (+)-lyoniresinol from wood

Journal of Wood Science volume 53, pages 161–167 (2007)Cite this article

Abstract

Steps leading to the biosynthesis of syringyl lignans and tetrahydronaphthalene and naphthalene lignans, especially the formation of the C2–C7′ linkage, have not been elucidated. Lyoniresinol is a typical syringyl lignan, as well as a tetrahydronaphthalene lignan found in Lyonia ovalifolia var. elliptica. To demonstrate the biosynthetic pathway for (+)-lyoniresinol, three putative biosynthetic intermediates of lyoniresinol, syringaresinol, 5,5′-dimethoxylariciresinol, and 5,5′-dimethoxysecoisolariciresinol, were isolated from wood. The identity of the putative intermediates was confirmed by spectroscopic analyses, as well as by comparison of spectral and chromatographic data with those of authentic samples previously synthesized. The stereochemistry (enantiomeric composition and absolute configuration) of the isolated lignans were determined as (±)-syringaresinol, (8S,8′S)-(−)-5,5′-dimethoxylariciresinol [46% enantiomeric excess (e.e.)], (8S,8′S)-(+)-5,5′-dimethoxysecoisolariciresinol (91% e.e.), and (8R,8′R)-(+)-lyoniresinol (42% e.e.). The absolute configurations of (+)-and (-)-5,5′-dimethoxylariciresinols, and (+)-and (-)-5,5′-dimethoxysecoisolariciresinols were determined by their synthesis (catalytic reduction) from (8R,8′R)-(+)-and (8S,8′S)-(-)-syringaresinols and by subsequent chiral high-performance liquid chromatography analysis.

References

  1. Azhar-ul-Haq, Malik A, Khan MTH, Anwar-ul-Haq, Khan SB, Ahmad A, Choudhary MI (2006) Tyrosinase inhibitory lignans from the methanol extract of the roots of Vitex negundo Linn. and their structure-activity relationship. Phytomedicine 13:255–260

    Article  CAS  PubMed  Google Scholar 

  2. Yasue M, Kato Y (1960) Structure of lyoniside. J Pharm Soc Jpn 80:1013–1014

    Article  CAS  Google Scholar 

  3. Kato Y, Kato N, Baba M (1984) Phenolic constituents of Lyonia ovalifolia. Pharmazie 39:425–426

    CAS  Google Scholar 

  4. Kato Y (1963) Structure of lyoniresinol (dimethoxyisolariciresinol). Chem Pharm Bull 11:823–827

    Article  CAS  PubMed  Google Scholar 

  5. Umezawa T, Davin LB, Yamamoto E, Kingston DGL, Lewis NG (1990) Lignan biosynthesis in Forsythia species. J Chem Soc Chem Commun 1405-1408

  6. Davin LB, Bedgar DL, Katayama T, Lewis NG (1992) On the stereoselective synthesis of (+)-pinoresinol in Forsythia suspensa from its achiral precursor, coniferyl alcohol. Phytochemistry 31:3869–3874

    Article  CAS  PubMed  Google Scholar 

  7. Katayama T, Davin LB, Lewis NG (1992) An extraordinary accumulation of (-)-pinoresinol in cell-free extracts of Forsythia intermedia: evidence for enantiospecific reduction of (+)-pinoresinol. Phytochemistry 31:3875–3881

    Article  CAS  PubMed  Google Scholar 

  8. Katayama T, Davin LB, Chu A, Lewis NG (1993) Novel benzylic ether reductions in lignan biogenesis in Forsythia intermedia. Phytochemistry 33:581–591

    Article  CAS  Google Scholar 

  9. Dinkova-Kostova AT, Gang DR, Davin LB, Bedgar DL, Chu A, Lewis NG (1996) (+)-Pinoresinol/(+)-lariciresinol reductase from Forsythia intermedia: protein purification, cDNA cloning, heterologous expression and comparison to isoflavone reductase. J Biol Chem 271:29473–29482

    Article  CAS  PubMed  Google Scholar 

  10. Davin LB, Wang HB, Crowell AL, Bedgar DL, Martin DM, Sarkanen S, Lewis NG (1997) Stereoselective bimolecular phenoxy radical coupling by an auxiliary (dirigent) protein without an active center. Science 275:362–366

    Article  CAS  PubMed  Google Scholar 

  11. Broomhead AJ, Rahman MMA, Dewick PM, Jackson DE, Lucas JA (1991) Matairesinol as precursor of Podophyllum lignans. Phytochemistry 30:1489–1492

    Article  CAS  Google Scholar 

  12. Xia ZQ, Costa MA, Proctor J, Davin LB, Lewis NG (2000) Dirigent-mediated podophyllotoxin biosynthesis in Linum flavum and Podophyllum peltatum. Phytochemistry 55:537–549

    Article  CAS  PubMed  Google Scholar 

  13. Weinges K (1961) Über einige neue Lignane und stereochemische Zusammenhänge in der Lignangruppe. Chem Ber 94:2522–2533

    Article  CAS  Google Scholar 

  14. Sakakibara J, Ina H, Yasue M (1974) Studies on the constituents of Tripetaleia paniculata Sieb. et Zucc. IV. On the constituents of the wood. (2). Structure of lyoniside (in Japanese). Yakugaku Zasshi 94:1377–1383

    Article  CAS  PubMed  Google Scholar 

  15. Miyamura M, Nohara T, Tomimatsu T, Nishioka I (1983) Seven aromatic compounds from bark of Cinnamomum cassia. Phytochemistry 22:215–218

    Article  CAS  Google Scholar 

  16. Narasimhachari N, Von Rudloff E (1973) Lyoniside and aucuparins from wood of North American Sorbus species. Phytochemistry 12:2551–2552

    Article  CAS  Google Scholar 

  17. Narasimhachari N, Von Rudloff E (1962) The chemical composition of the wood extractives of Sorbus decora (Sarg.) Schneid. Can J Chem 40:1118–1122

    Article  CAS  Google Scholar 

  18. Raju GVS, Pillai KR (1989) Lignans from Justicia tranquebariensis Linn. f. Ind J Chem 28B:558–561

    CAS  Google Scholar 

  19. Nabeta K, Yonekubo J, Miyake M (1987) Phenolic compounds from the heartwood of European oak (Quercus robur L.) and Brandy. Mokuzai Gakkaishi 33:408–415

    CAS  Google Scholar 

  20. Hostettler FD, Seikel MK (1969) Lignans of Ulmus thomasii heartwood-II. Lignans related to thomasic acid. Tetrahedron 25:2325–2337

    Article  CAS  PubMed  Google Scholar 

  21. Vecchietti V, Ferrari G, Orsini F, Pelizzoni F (1979) Alkaloid and lignan constituents of Cinnamosma madagascariensis. Phytochemistry 18:1847–1849

    Article  CAS  Google Scholar 

  22. Varma M, Varma RS, Parthasarathy MR (1980) Minor phenolic constituents of Grevillea robusta and Hakea saligna. Z Naturforsch C 35:344–345

    Google Scholar 

  23. Ida Y, Satoh Y, Ohtsuka M, Nagasao M, Shoji J (1994) Phenolic constituents of Phellodendron amurense bark. Phytochemistry 35:209–215

    Article  CAS  Google Scholar 

  24. Chandel RS, Rastogi RP (1980) Pygeoside, a new lignan xyloside from Pygeum acuminatum. Ind J Chem 19B:279–282

    CAS  Google Scholar 

  25. Quideau S, Ralph J (1992) Facile large-scale synthesis of coniferyl, sinapyl and p-coumaryl alcohol. J Agric Food Chem 40:1108–1110

    Article  CAS  Google Scholar 

  26. Katayama T, Masaoka T (1997) Biosynthesis and stereochemistry of lignans in Zanthoxylum ailanthoides. I. (+)-Lariciresinol formation by enzymatic reduction of (±)-pinoresinols. Mokuzai Gakkaishi 43:580–588

    CAS  Google Scholar 

  27. Katayama Y, Fukuzumi T (1978) Enzymatic synthesis of three lignin-related dimers by an improved peroxidase-hydrogen peroxide system (in Japanese). Mokuzai Gakkaishi 24:664–667

    CAS  Google Scholar 

  28. Erdtman H, Gripenberg J (1947) Die Konstitution der Harzphenole und ihre biogenetischen Zusammenhänge. X. Herausspaltung des “Mittelstückes” des Pinoresinols. Acta Chem Scand 1:71–75

    Article  CAS  PubMed  Google Scholar 

  29. Freudenberg K, Sidhu GS (1961) Die absolute Konfiguration der Gruppe des Sesamins und Pinoresinols. Chem Ber 94:851–862

    Article  CAS  Google Scholar 

  30. Kato Y (1966) The absolute configuration of lyoniresinol. Chem Pharm Bull 14:1438–1439

    CAS  Google Scholar 

Download references

Author information

Authors and Affiliations

  1. Faculty of Agriculture, Kagawa University, 2393 Ikenobe, Miki-cho, Kagawa, 761-0795, Japan

    MD. Atiar Rahman, Takeshi Katayama, Toshisada Suzuki & Takashi Nakagawa

Authors
  1. MD. Atiar Rahman
    View author publications

    You can also search for this author in PubMed Google Scholar

  2. Takeshi Katayama
    View author publications

    You can also search for this author in PubMed Google Scholar

  3. Toshisada Suzuki
    View author publications

    You can also search for this author in PubMed Google Scholar

  4. Takashi Nakagawa
    View author publications

    You can also search for this author in PubMed Google Scholar

Corresponding author

Correspondence to Takeshi Katayama.

Additional information

This report was presented at the 55th Annual Meeting of the Japan Wood Research Society, Kyoto, March 2005

Rights and permissions

Reprints and permissions

About this article

Cite this article

Rahman, M.A., Katayama, T., Suzuki, T. et al. Stereochemistry and biosynthesis of (+)-lyoniresinol, a syringyl tetrahydronaphthalene lignan in Lyonia ovalifolia var. elliptica I: isolation and stereochemistry of syringyl lignans and predicted precursors to (+)-lyoniresinol from wood. J Wood Sci 53, 161–167 (2007). https://doi.org/10.1007/s10086-006-0832-1

Download citation

  • Received:

  • Accepted:

  • Published:

  • Issue Date:

  • DOI: https://doi.org/10.1007/s10086-006-0832-1

Key words