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

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.