The intriguing dual-directing effect of 2-cyanobenzyl ether for a highly stereospecific glycosylation reaction

The diverse presence as well as their very specific bio-responses of glycoconjugates found in all living species requires scientists to synthesize the precise structure of these complex oligosaccharides for various studies on glycoscience. Very few approaches were able to offer the sole α- or β-glyc...

Full description

Saved in:
Bibliographic Details
Published in:Nature communications 2014-10, Vol.5 (1), p.5051-10, Article 5051
Main Authors: Le Mai Hoang, Kim, Liu, Xue-Wei
Format: Article
Language:English
Subjects:
140/131
639/638/403/934
639/638/403/935
Carbohydrates
Chemistry
Ether - chemistry
Ethers
Glycoconjugates
Glycoconjugates - chemistry
Glycosides - chemistry
Glycosylation
Humanities and Social Sciences
Isomers
Magnetic Resonance Spectroscopy
Methylene Chloride - chemistry
multidisciplinary
NMR
Nuclear magnetic resonance
Oligosaccharides
Organic Chemicals - chemistry
Science
Solvents
Solvents - chemistry
Stereoisomerism
Stereoselectivity
Temperature
Toluene - chemistry
Citations: Items that this one cites
Items that cite this one
Online Access:Get full text
Tags: Add Tag
No Tags, Be the first to tag this record!
Description
Summary:The diverse presence as well as their very specific bio-responses of glycoconjugates found in all living species requires scientists to synthesize the precise structure of these complex oligosaccharides for various studies on glycoscience. Very few approaches were able to offer the sole α- or β-glycosylated products, even at the cost of complicating the preparative route or usage of exotic chiral auxiliaries to drive the stereoselectivity. In this report, the unification of solvent assistance and neighbouring group participation concepts have led us to the use of 2-cyanobenzyl ether as the dual-directing auxiliary for stereospecific construction of α- and β-glycosidic bonds from a single starting material, and both isomers can be obtained in exclusive stereoselectivity. This work demonstrates the difference in reactivities of glycosyl acceptors can be employed to completely drive the stereoselectivity, drawing the parallel comparison with the arming/disarming concept, which has been exclusively confined to glycosyl donors. Glycosylation reactions can be hampered by a lack of selectivity, giving mixtures of α- and β-products. Here, the authors demonstrate the use of 2-cyanobenzyl functionalization as a directing group to give α- or β-selectivity from a single starting material.
ISSN:2041-1723
2041-1723
DOI:10.1038/ncomms6051