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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 |
Discipline: | Chemistry |
Degree Granting Institution: | University of Illinois at Urbana-Champaign |
Degree: | Ph.D. |
Genre: | Dissertation |
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 |
Type: | Text |
Language: | English |
Description: | 272 p. Thesis (Ph.D.)--University of Illinois at Urbana-Champaign, 2003. |
URI: | http://hdl.handle.net/2142/84118 |
Other Identifier(s): | (MiAaPQ)AAI3101910 |
Date Available in IDEALS: | 2015-09-25 |
Date Deposited: | 2003 |
This item appears in the following Collection(s)
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Dissertations and Theses - Chemistry
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Graduate Dissertations and Theses at Illinois
Graduate Theses and Dissertations at Illinois