天然存在的苄基 6-O-糖基-β-D-吡喃葡萄糖苷的化学酶法合成

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

作者信息

Kawahara Eiji, Fujii Mikio, Kato Keisuke, Ida Yoshiteru, Akita Hiroyuki

机构信息

School of Pharmaceutical Sciences, Toho University, 2-2-1 Miyama, Funabashi, Chiba 274-8510, Japan.

出版信息

Chem Pharm Bull (Tokyo). 2005 Aug;53(8):1058-61. doi: 10.1248/cpb.53.1058.

DOI:10.1248/cpb.53.1058

PMID:16079550

Abstract

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 beta-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-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.

摘要

使用杏仁固定化β-葡萄糖苷酶与合成预聚物ENTP-4000，使苯甲醇与D-葡萄糖（5）直接进行β-葡萄糖苷化反应，得到苄基β-D-葡萄糖苷（1），产率为53%。由1衍生的苄基β-D-吡喃葡萄糖苷同系物（8）与苯基2,3,4-三-O-乙酰基-1-硫代-β-D-吡喃木糖苷（9）、乙基2,3,4-三-O-乙酰基-1-硫代-α-L-吡喃鼠李糖苷（13）以及2,3,4-三-O-乙酰基-α-L-吡喃阿拉伯糖基溴（15）进行偶联反应，分别得到偶联产物10、14和16。对10、14和16进行脱保护反应，分别得到合成的苄基β-D-吡喃木糖基-（1→6）-β-D-吡喃葡萄糖苷（2）、苄基α-L-吡喃鼠李糖基-（1→6）-β-D-吡喃葡萄糖苷（3）以及苄基α-L-吡喃阿拉伯糖基-（1→6）-β-D-吡喃葡萄糖苷（4）。