3.3 Further Anomeric Esters
Kwan Soo Kim, Heung Bae Jeon
Center for Bioactive Molecular Hybrids and Department of Chemistry, Yonsei
University, Seoul 120–749, Korea
kwan@yonsei.ac.kr
1 Introduction . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 526
2 Glycosylation with Glycosyl Acetates . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 526
3 Glycosylation with Donors Having Other Anomeric Ester Groups . . . . . . . . . . . . . . 544
4 Glycosylation with Glycosyl Carbonates and Related Donors . . . . . . . . . . . . . . . . . . . 551
5 Intramolecular Glycosylation Through 1-O-Acyl Linkages . . . . . . . . . . . . . . . . . . . . . 556
6 Glycosylation with Donors Having Remote Acyl Groups . . . . . . . . . . . . . . . . . . . . . . . . 558
Abstract
The most representative anomeric ester glycosyl donor is glycosyl acetate, which seems to be
a promising and useful glycosylating reagent due to a variety of advantageous properties. Several other anomeric acyl and carbonate-type leaving groups have been devised as new glycosyl
donors. In particular, the glycosyl acetate can be the precursor for glycosylating agents of other types, for example, glycosyl halides, 1-thioglycosides, and glycosyl trichloroacetimidates.
Therefore, use of glycosyl acetate can make glycosylation reactions easier and less expensive.
Furthermore, the intramolecular glycosylation method through the 1-O-acyl linkage and the
glycosylation with glycosyl donors having remote acyl groups from the anomeric center have
been developed to increase the efficiency and the stereoselectivity.
Keywords
Glycosylation; Glycosyl donor; Anomeric leaving group; Anomeric ester; Glycosyl acetate;
Glycosyl carbonate; 1-O-acyl linkage; Remote acyl group
Abbreviations
CB
2 -carboxybenzyl
DCC
1,3-dicyclohexylcarbodiimide
DIC
diisopropylcarbodiimide
Dmob
N-2,4-dimethoxybenzyl
IDCP
iodonium dicollidine perchlorate
LPS
lipopolysaccharide
NIS
N-iodosuccinimide
TBSOTf tert-butyldimethylsilyl trifluoromethanesulfonate
TMSOTf trimethylsilyl trifluoromethanesulfonate
In: Glycoscience. Fraser-Reid B, Tatsuta K, Thiem J (eds)
Chapter-DOI 10-1007/978-3-540-30429-6_12: © Springer-Verlag Berlin Heidelberg 2008
Kwan Soo Kim, Heung Bae Jeon
Center for Bioactive Molecular Hybrids and Department of Chemistry, Yonsei
University, Seoul 120–749, Korea
kwan@yonsei.ac.kr
1 Introduction . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 526
2 Glycosylation with Glycosyl Acetates . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 526
3 Glycosylation with Donors Having Other Anomeric Ester Groups . . . . . . . . . . . . . . 544
4 Glycosylation with Glycosyl Carbonates and Related Donors . . . . . . . . . . . . . . . . . . . 551
5 Intramolecular Glycosylation Through 1-O-Acyl Linkages . . . . . . . . . . . . . . . . . . . . . 556
6 Glycosylation with Donors Having Remote Acyl Groups . . . . . . . . . . . . . . . . . . . . . . . . 558
Abstract
The most representative anomeric ester glycosyl donor is glycosyl acetate, which seems to be
a promising and useful glycosylating reagent due to a variety of advantageous properties. Several other anomeric acyl and carbonate-type leaving groups have been devised as new glycosyl
donors. In particular, the glycosyl acetate can be the precursor for glycosylating agents of other types, for example, glycosyl halides, 1-thioglycosides, and glycosyl trichloroacetimidates.
Therefore, use of glycosyl acetate can make glycosylation reactions easier and less expensive.
Furthermore, the intramolecular glycosylation method through the 1-O-acyl linkage and the
glycosylation with glycosyl donors having remote acyl groups from the anomeric center have
been developed to increase the efficiency and the stereoselectivity.
Keywords
Glycosylation; Glycosyl donor; Anomeric leaving group; Anomeric ester; Glycosyl acetate;
Glycosyl carbonate; 1-O-acyl linkage; Remote acyl group
Abbreviations
CB
2 -carboxybenzyl
DCC
1,3-dicyclohexylcarbodiimide
DIC
diisopropylcarbodiimide
Dmob
N-2,4-dimethoxybenzyl
IDCP
iodonium dicollidine perchlorate
LPS
lipopolysaccharide
NIS
N-iodosuccinimide
TBSOTf tert-butyldimethylsilyl trifluoromethanesulfonate
TMSOTf trimethylsilyl trifluoromethanesulfonate
In: Glycoscience. Fraser-Reid B, Tatsuta K, Thiem J (eds)
Chapter-DOI 10-1007/978-3-540-30429-6_12: © Springer-Verlag Berlin Heidelberg 2008