Isoquinoline‐1‐Carboxylate as a Traceless Leaving Group for Chelation‐Assisted Glycosylation under Mild and Neutral Reaction Conditions

Glycosyl isoquinoline‐1‐carboxylate was developed as a novel benchtop stable and readily available glycosyl donor. The glycosylation reaction was promoted by the inexpensive Cu(OTf)2 salt under mild reaction conditions. The copper isoquinoline‐1‐carboxylate salt was precipitated from the solution an...

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Bibliographic Details
Published in:Angewandte Chemie International Edition 2017-12, Vol.56 (49), p.15698-15702
Main Authors: Wang, Hao‐Yuan, Simmons, Christopher J., Blaszczyk, Stephanie A., Balzer, Paul G., Luo, Renshi, Duan, Xiyan, Tang, Weiping
Format: Article
Language:English
Subjects:
carbohydrates
chelates
Chelation
Coordination compounds
Copper
Glycosylation
Gold
Oligosaccharides
pH effects
Salts
synthetic methods
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Summary:Glycosyl isoquinoline‐1‐carboxylate was developed as a novel benchtop stable and readily available glycosyl donor. The glycosylation reaction was promoted by the inexpensive Cu(OTf)2 salt under mild reaction conditions. The copper isoquinoline‐1‐carboxylate salt was precipitated from the solution and thus rendered a traceless leaving group. Surprisingly, the proton from the acceptor was absorbed by the precipitated metal complex and the reaction mixture remained at neutral pH. The copper‐promoted glycosylation was also proven to be completely orthogonal to the gold‐promoted glycosylation, and an iterative synthesis of oligosaccharides from benchtop stable anomeric ester building blocks becomes possible under mild reaction conditions. Generous donor: A new glycosyl ester donor was developed. It is readily available, benchtop stable, reactive upon chelation to inexpensive copper salts under mild and neutral reaction conditions, orthogonal to other glycosyl esters, serves as a traceless leaving group, and facilitates a broad substrate scope. Tf=trifluoromethanesulfonyl.
ISSN:1433-7851
1521-3773
DOI:10.1002/anie.201708920