Skip to main content
Journal of Wood Science

Official Journal of the Japan Wood Research Society

Download PDF
  • Original Article
  • Published:

Role of caffeic glucoside esters in defense-repair processing of trees II: Synthesis of 2-(3,4-dihydroxyphenyl)-ethyl 3-α-L-rhamnopyranosylβ-D-glucopyranoside

Journal of Wood Science volume 44, pages 320–326 (1998)Cite this article

Abstract

The reference compound (9), with a partial structure of acteoside, was synthesized to elucidate the relation between structural features and the precipitation or solubility of the oxidation products of acteoside: 2-(3,4-dihydroxyphenyl)-ethyl 3-O-(α-L-rhamnopyranosyl)-β-D-glucopyranoside (9). The glycosyl acceptor 2-O-benzoyl-3-O-(2,3,4-tri-O-acetyl-α-L-rhamnopyranosyl)-4,6-O-benzylidene-α-D-glucopyranosyl trichloroacetimidate (7) was prepared from allyl 2-O-benzoyl-3-O-(2,3,4-tri-O-acetyl-α-L-rhamnopyranosyl)-4,6-O-benzylidene-α-D-glucopyranoside (4) via isomerization of the allyl group with an iridium complex to the 1-propenyl group and its hydrolysis with HgCl2lHgO, followed by treatment with CCl3CN and DBU in a 65.5% overall yield. The glycosyl acceptor 3,4-diacetoxyphenethyl alcohol (16) was prepared from homoveratric acid via demethylation with 57% HI and its acetylation with Ac2O and 85% H3PO4, followed by selective reduction of the carboxyl group to the alcohol with a borane-tetrahydrofurane complex in a 61% overall yield. The glycosylation of7 with16 in dichloromethane promoted by BF3-Et2O gave a 74.3% yield of8. Hydrolysis of8 with 90% CF3COOH gave the debenzylidenated product, which was treated with NaOMe to afford a 32% overall yield of the desired compound9. This compound9 was identical with the natural specimen.

References

  1. Ota M, Azuma T, Ohira M, Abe K, Kofujita H (1997) Role of caffeic glucoside esters in defense-repair processing of trees. I. Synthesis of the partial structure of acteoside, 2-(3,4-dihydroxypheny)-ethylβ-D-glucopyranoside, and peroxidasecatalyzed oxidation. Mokuzai Gakkaishi 43:260–267

    CAS  Google Scholar 

  2. Li ZJ, Huang HQ, Cai MS (1994) Facile synthesis of the sugar cores from phenylpropanoid glycosides. Carbohydr Res 265:227–236

    Article  CAS  PubMed  Google Scholar 

  3. Yamada H, Harada T, Takahashi T (1994) Synthesis of an elicitoractive hexaglucoside analogue by a one-pot, two-step glycosidation procedure. J Am Chem Soc 116:7919–7920

    Article  CAS  Google Scholar 

  4. Harada T, Yamada H, Tsukamoto H, Takahashi T (1995) Allyoxycarbonyl group as a protective group for the hydroxyl group in carbohydrates. J Carbohydr Chem 14:165–170

    Article  CAS  Google Scholar 

  5. Nishibe S, Murai M (1995) Bioactive components of plantago herb (in Japanese). FFI J 166:43–49

    CAS  Google Scholar 

  6. Pan N, Hori H (1996) Antioxidant action of acteoside and its analogs on lipid peroxidation. Redox Rep 2:149–154

    Article  CAS  PubMed  Google Scholar 

  7. Xiong Q, Kadota S, Tani T, Namba T (1996) Antioxidative effects of phenylethanoids from Cistanche deserticola. Biol Pharm Bull 19:1580–1585

    Article  CAS  PubMed  Google Scholar 

  8. Pelyvás I, Lindhorst T, Thiem J (1990) En route to thromboxane compounds from carbohydrates. I. Synthesis of the unsaturated sugar precursors. Liebigs Ann Chem 761–769

  9. Kim S, Chang H, Kim WJ (1985) Selective benzoylation of diols with 1-(benzoyloxy)benzotriazole. J Org Chem 50:1751–1752

    Article  CAS  Google Scholar 

  10. Oltvoort JJ, van Boeckel CAA, de Koning JH, van Boom JH (1981) Use of the cationic iridium complex 1,5-cyclooctadienebis[methyldiphenylphosphine]-iridium hexalluorophosphate in carbohydrate chemistry: smooth isomerization of allyl ethers to 1-propenyl ethers. Synthesis 305–308

  11. Baudry D, Ephritikhine M, Felkin H (1978) Isomerisation of allyl ethers catalysed by the cationic iridium complex [Ir(cyclo-octa-1,5-diene)(PMePh2)2]PF6: a highly stereoselective route totrans-propenyl ethers. J Chem Soc Chem Commun 694–695

  12. Gigg R, Warren CD (1968) The allyl ether as a protecting group in carbohydrate chemistry. Part 11. J Chem Soc (C) 1903–1911

  13. Schmidt RR, Michel J (1985) O-(α-D-Glucopyranosyl) trichloroacetimidate as a glucosyl donor. J Carbohydr Chem 4:141–169

    Article  CAS  Google Scholar 

  14. Kawada T, Nakatubo F, Murakami K (1989) Synthetic studies of cellulose. IV. Preparation of perbenzylated allyl 4′-O-p-methoxybenzyl cellobioside by the imidate method. Mokuzai Gakkaishi 35:21–25

    CAS  Google Scholar 

  15. Excoffier G, Gagnaire D, Utille JP (1975) Coupure sélective par l'hydrazine des groupements acétyles anoméres de résidus glycosyles acétylés. Carbohydr Res 39:368–373

    Article  CAS  Google Scholar 

  16. Yoon NM, Pak CS, Brown HC, Krishnamurthy S, Stocky TP (1973) Selective reductions. XIX. The rapid reaction of carboxylic acids with borane-tetrahydrofuran: a remarkably convenient procedure for the selective conversion of carboxylic acids to the corresponding alcohols in the presence of other functional groups. J Org Chem 38:2786–2792

    Article  CAS  Google Scholar 

  17. Burger JFW, Brandt EV, Ferreira D (1987) Iridoid and phenolic glycosides fromHarpagophytum procumbens. Phytochemistry 26:1453–1457

    Article  CAS  Google Scholar 

  18. Nishimura H, Sasaki H, Morota T, Chin M (Zhengxiong C) Mitsuhashi H (1990) Six glycosides fromRehmannia glutinosa var.purpurea. Phytochemistry 29:3303–3306

    Article  CAS  Google Scholar 

  19. Zimin L, Zhongjian J (1991) Phenylpropanoid and iridoid glycosides fromPedicularis striata. Phytochemistry 30:1341–1344

    Article  Google Scholar 

  20. Gräwe W, Strack D (1986) Partial purification and some properties of 1-sinapoylglucose: choline sinapoyltransferase (“sinapine synthase”) from seeds ofRaphanus sativus L. andSinapis alba L. Z Naturforsch 41c:28–33

    Google Scholar 

  21. Hohlfeld M, Veit M, Strack D (1996) Hydroxycinnamoyltransferases involved in the accumulation of caffeic esters in gametophytes and sporophytes ofEquisetum arvense. Plant Physiol 111:1153–1159

    Article  CAS  PubMed  PubMed Central  Google Scholar 

Download references

Author information

Authors and Affiliations

  1. Faculty of Agriculture, Department of Bioscience and Technology, Iwate University, 020-8550, Morioka, Japan

    Michikazu Ota & Hisayoshi Kofujita

  2. Faculty of Agriculture, Department of Bioenvironment, Yamagata University, 997-8555, Tsuruoka, Japan

    Kouetsu Takahashi

Authors
  1. Michikazu Ota
    View author publications

    You can also search for this author in PubMed Google Scholar

  2. Kouetsu Takahashi
    View author publications

    You can also search for this author in PubMed Google Scholar

  3. Hisayoshi Kofujita
    View author publications

    You can also search for this author in PubMed Google Scholar

Corresponding author

Correspondence to Michikazu Ota.

Rights and permissions

Reprints and permissions

About this article

Cite this article

Ota, M., Takahashi, K. & Kofujita, H. Role of caffeic glucoside esters in defense-repair processing of trees II: Synthesis of 2-(3,4-dihydroxyphenyl)-ethyl 3-α-L-rhamnopyranosylβ-D-glucopyranoside. J Wood Sci 44, 320–326 (1998). https://doi.org/10.1007/BF00581314

Download citation

  • Received:

  • Accepted:

  • Published:

  • Issue Date:

  • DOI: https://doi.org/10.1007/BF00581314

Key words