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Title:C2-Amidoglycosylation With Glycal Donors for the Synthesis of 2-N-Acylamino-2-Deoxypyranosides. Development, Scope, and Mechanism
Author(s):Liu, Jing
Doctoral Committee Chair(s):Gin, David Y.
Department / Program:Chemistry
Degree Granting Institution:University of Illinois at Urbana-Champaign
Subject(s):Chemistry, Organic
Abstract:A one-pot C2-amidoglycosylation reaction for the synthesis of 2-N-acylamino-2-deoxypyranosides from glycal donors has been developed. In the reaction, activation of glycal donor by a sulfoxide and triflic anhydride followed by regio- and stereoselective transfer of an amide nucleophile generates an oxazoline intermediate, which can glycosylate a wide variety of nucleophiles in situ to provide the corresponding C2-amidoglycosides. C2-Acetamidoglycosylation with glucals using N-(TMS)acetamide for the first time affords the naturally occuring 2-N-acetylamino-2-deoxypyranoses in a one-pot procedure. The diastereoselectivity of the C2-amidoglycosylation reaction can be controlled by the choice of sulfoxide reagent, and C2-amidosugars derived from glucose, mannose, and galactose can all be synthesized. Tracking of the reaction by low temperature NMR spectroscopy employing isotope-labeled substrates suggests a mechanism involving the formation of a C2-sulfonium glycosyl imidate as the key intermediate in the nitrogen transfer process.
Issue Date:2003
Description:272 p.
Thesis (Ph.D.)--University of Illinois at Urbana-Champaign, 2003.
Other Identifier(s):(MiAaPQ)AAI3101910
Date Available in IDEALS:2015-09-25
Date Deposited:2003

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