The Stereodirecting Effect of the Glycosyl C5-Carboxylate Ester: Stereoselective Synthesis of β-Mannuronic Acid Alginates

被引：67

作者：

Codee, Jeroen D. C. ^{[1
]}

van den Bos, Leendert J. ^{[1
]}

de Jong, Ana-Rae ^{[1
]}

Dinkelaar, Jasper ^{[1
]}

Lodder, Gerrit ^{[1
]}

Overkleeft, Herman S. ^{[1
]}

van der Marel, Gijsbert A. ^{[1
]}

机构：

[1] Leiden Univ, Leiden Inst Chem, NL-2300 RA Leiden, Netherlands

来源：

JOURNAL OF ORGANIC CHEMISTRY | 2009年 / 74卷 / 01期

关键词：

DIRECT CHEMICAL-SYNTHESIS; OLIGOSACCHARIDE SYNTHESIS; ALPHA-GLUCOPYRANOSYLATION; SULFOXIDE METHOD; URONIC-ACIDS; MANNOPYRANOSIDES; DONORS; THIOGLYCOSIDES; IONS; HYDROLYSIS;

D O I：

10.1021/jo8020192

中图分类号：

O62 [有机化学];

学科分类号：

070303 ; 081704 ;

摘要：

Glycosylations of mannuronate ester donors proceed highly selectively to produce the 1,2-cis-linked products. We here forward a mechanistic rationale for this counterintuitive selectivity, based oil the remote stereodirecting effect of the C5-carboxylate ester, which has been demonstrated using pyranosyl uronate ester devoid of ring substituents other than the C5-carboxylate ester. It is postulated that the C5-carboxylate ester prefers to occupy an axial position in the oxacarbenium intermediate, thereby favoring the formation of the H-3(4) half-chair over the H-4(3) conformer Nucleophilic attack oil the H-3(4) half-chair intermediate occurs in a beta-fashion, providing the 1,2-cis-mannuronates with excellent stereoselectivity. The potential of the mannuronate ester donors in the formation of the beta-mannasidic linkage has been capitalized upon in the construction of a mannuronic acid alginate pentamer using a convergent orthogonal glycosylation strategy.

引用

页码：38 / 47

页数：10

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