文章基本信息

标题：β-Selective Glycosylation Using Axial-Rich and 2-O-Rhamnosylated Glucosyl Donors Controlled by the Protecting Pattern of the Second Sugar
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作者：Masafumi Bando ; Yuri Kawasaki ; Osamu Nagata 等
期刊名称：Chemical and Pharmaceutical Bulletin
印刷版ISSN：0009-2363
电子版ISSN：1347-5223
出版年度：2021
卷号：69
期号：1
页码：124-140
DOI：10.1248/cpb.c20-00733
出版社：The Pharmaceutical Society of Japan
摘要：Herein, we describe two counterexamples of the previously reported β/α-selectivity of 96/4 for glycosylation using ethyl 2- O -[2,3,4-tris- O - tert -butyldimethylsilyl (TBS)-α-L-rhamnopyranosyl]-3,4,6-tris- O -TBS-thio-β-D-glucopyranoside as the glycosyl donor. Furthermore, we investigated the effects of protecting group on the rhamnose moieties in the glycosylation with cholestanol and revealed that β-selectivity originated from the two TBS groups at the 3-O and 4-O positions of rhamnose. In contrast, the TBS group at the 2-O position of rhamnose hampered the β-selectivity. Finally, the β/α-selectivity during the glycosylation was enhanced to ≥99/1. The results obtained herein suggest that the protecting groups on the sugar connected to the 2-O of a glycosyl donor with axial-rich conformation can control the stereoselectivity of glycosylation.
关键词：2-O-ramnosylated glucose donor;β-selective glycosylation;axial-rich;bulky silyl group;protecting group effect