Protecting Group Dependence of Stereochemical Outcome of Glycosylation of 2-O-(Thiophen-2-yl)methyl Ether Protected Glycosyl Donors

被引：10

作者：

Watson, Andrew J. A. ^{[1
]}

Alexander, Stewart R. ^{[1
]}

Cox, Daniel J. ^{[3
]}

Fairbanks, Antony J. ^{[1
,2
]}

机构：

[1] Univ Canterbury, Dept Chem, Private Bag 4800, Christchurch 8140, New Zealand

[2] Univ Canterbury, Biomol Interact Ctr, Private Bag 4800, Christchurch 8140, New Zealand

[3] Univ Oxford, Chem Res Lab, Dept Chem, Mansfield Rd, Oxford OX1 3TA, England

来源：

EUROPEAN JOURNAL OF ORGANIC CHEMISTRY | 2016年 / 2016卷 / 08期

基金：

英国工程与自然科学研究理事会;

关键词：

Protecting groups; Neighbouring group participation; Glycosylation; Diastereoselectivity; INTRAMOLECULAR AGLYCON DELIVERY; NEIGHBORING-GROUP PARTICIPATION; STEREOCONTROLLED SYNTHESIS; STEREOSELECTIVE-SYNTHESIS; ALPHA-GLUCOSIDES; STEREOSPECIFIC SYNTHESIS; 1,2-CIS GLYCOSYLATION; SULFONIUM IONS; OLIGOSACCHARIDES; STRATEGY;

D O I：

10.1002/ejoc.201600071

中图分类号：

O62 [有机化学];

学科分类号：

070303 ; 081704 ;

摘要：

A series of glycosyl donors possessing a (thiophen2-yl) methyl ether protecting group at position 2 were synthesised and the effect of the protecting group pattern of other hydroxyls on the stereochemical outcome of glycosylation was investigated. Studies revealed optimal a-selectivity for glycosylation using a fully armed tri-benzylated donor, whilst other protecting group patterns were significantly less effective. Lowtemperature NMR studies of both fully armed and fully disarmed donors revealed the intermediacy of cyclised sulfonium ion intermediates. Reaction conditions were developed which allowed removal of the (thiophen-2-yl) methyl ether protecting group either selectively, or together with benzyl ethers.

引用

页码：1520 / 1532

页数：13