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Journal of Wood Science

Official Journal of the Japan Wood Research Society

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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.

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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
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  2. Kouetsu Takahashi
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  3. Hisayoshi Kofujita
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Correspondence to Michikazu Ota.

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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

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Key words

  • Synthesis
  • Acteoside
  • 2-(3,4-Dihydroxyphenyl)-ethyl
  • 3-O-(α-L-rhamnopyranosyl)-β-D-glucopy-ranoside
  • 3,4-Diacetoxyphenethyl alcohol
  • Trichloroacetimidate method