First and efficient synthesis of 4-[((3,4-dihydroxybenzoyl)-oxy)methyl]-phenyl-β-D-glucopyranoside, an antioxidant from Origanum vulgare

Abstract

4-(3,4-Dihydroxybenzoyloxymethyl)phenyl-O-β-D-glucopyranoside (DBPG, 1 ), a polyphenolic glycoside previously isolated from Oregano(Origanum vulgare L.) in 0.08% isolated yield, was synthesized in five chemical steps with 41.4% overall yield. First, 4-(hydroxymethylphenyl)-2,3,4,6-tetra-O-acetyl-b-D-glucopyranoside 4 was obtained in 53.2% yield by selective glycosylation of 4-hydroxybenzyl alcohol 3 with 2,3,4,6-tetra-O-acetyl-α-D-glucopyranosyl bromide 2 in a mixture of chlorobenzene and aqueous CsOH using triethylbenzylammonium chloride (TEBAC) as a phase transfer catalyst. Then, this product was esterified with 3,4-diacetoxylbenzoyl chloride 7 to generate 4-(3,4-diacetoxybenzoyloxy-methyl) phenyl 2,3,4,6-tetra-O-acetyl-b-D-glucopyranoside 8 in 95% yield. Finally, selectively global deacetylation of 8 was performed in a mixture of dibutyltin oxide and methanol under reflux to afford 1 in 94.8% yield.

Keywords

• 4-(3,4-dihydroxybenzoyloxymethyl)phenyl-O-β-D-glucopyranoside
• synthesis
• glycosylation
• antioxidant
• dibutyltin oxide