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. 2011 Feb 9;133(5):1597-602.
doi: 10.1021/ja110115a. Epub 2011 Jan 5.

Encouraging progress in the ω-aspartylation of complex oligosaccharides as a general route to β-N-linked glycopolypeptides

Ping Wang  1 , Xuechen Li, Jianglong Zhu, Jin Chen, Yu Yuan, Xiangyang Wu, Samuel J Danishefsky
Affiliations

Encouraging progress in the ω-aspartylation of complex oligosaccharides as a general route to β-N-linked glycopolypeptides

Ping Wang et al. J Am Chem Soc. .

Abstract

Described herein is a method for the joining of complex peptides to complex oligosaccharides via an N-linkage. The ω-aspartylation is conducted by coupling fully deprotected glycosylamine with a peptide containing a unique thioacid at the ω-aspartate carboxyl. In the presence of HOBT, under conditions that, in principle, allow for oxidation, complex components are combined in encouraging yields to produce structurally and stereochemically defined N-linked glycopolypeptides wherein the carbohydrate domain can be quite complex. Various mechanisms for oxidative coupling are proposed.

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Figures

Figure 1
Figure 1
Merger of glycan and peptide domains through aspartylation; undesired base-induced aspartimide formation.
Figure 2
Figure 2
Proposed base-free amide β-asparagine linkage through interception of a thio-FCMA (formimidate carboxylate mixed anhydride) intermediate.
Figure 3
Figure 3
Thioacid peptides 7–13.
Figure 4
Figure 4
Oligosaccharides 14–17.
Figure 5
Figure 5
Possible mechanisms for HOBT-mediated oxidation.
See this image and copyright information in PMC

References

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