Chemoenzymatic synthesis of naturally occurring benzyl 6-O-glycosyl-β-D-glucopyranosides

Direct beta-glucosidation between benzyl alcohol and D-glucose (5) using the immobilized beta-glucosidase from almonds with the synthetic prepolymer ENTP-4000 gave a benzyl beta-D-glucoside (1) in 53% yield. The coupling of the benzyl P-D-glucopyranoside congener (8) derived from 1 with phenyl 2,3,4-tri-O-acetyl-1-thio-beta-D-xylopyranoside (9), ethyl 2,3,4-tri-O-acetyl-1-thio-alpha-L-rhamnopyranoside (13), and 2,3,4-tri-O-acetyl-alpha-L-arabinopyranosyl bromide (15) afforded 10, 14, and 16, respectively, as coupled products. Deprotection of 10, 14, and 16 provided the synthetic benzyl beta l-D-xylopyranosyl-(1 -> 6)-beta-d-glucopyranoside (2), benzyl alpha-L-rhamnopyranosyl-(1 -> 6)-beta-D-glucopyranoside (3), and benzyl alpha-L-arabinopyranosyl-(1 -> 6)-beta-D-glucopyranoside (4), respectively.