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Hansen, SU, Dalton, CE, Barath, M, Kwan, G, Raftery, J, Jayson, GC, Miller, GJ ORCID: https://orcid.org/0000-0001-6533-3306 and Gardiner, JM (2015) Synthesis of L-Iduronic Acid Derivatives via [3.2.1] and [2.2.2] L-Iduronic Lactones from Bulk Glucose-Derived Cyanohydrin Hydrolysis: A Reversible Conformationally Switched Superdisarmed/Rearmed Lactone Route to Heparin Disaccharides. Journal Of Organic Chemistry, 80 (8). 3777 -3789.

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Abstract

l-Idofuranoside cyanohydrin 1 is converted on large scale into a mixture of l-IdoA methyl pyranosides and furanosides, which is converged to provide short 2-step routes to bicyclic [3.2.1] or [2.2.2] l-iduronate lactones. The former is obtained via a 100 g scale synthesis of 3-OBn l-IdoA. A two-step conversion of this mixture provides either pure anomer of the novel [2.2.2] l-iduronate thioglycoside lactones. Both [3.2.1] and [2.2.2] lactones are converted into GlcN-IdoA heparin precursor disaccharides. The [2.2.2] lactone enables a scalable 3-step route from 1 to a new type of highly disarmed O-4 iduronate thioglycoside, which is an effective acceptor with glucoazide thioglycoside donors. The resulting new iduronic [2.2.2] lactone disaccharides are readily rearmed by mild methanolysis to provide GlcN-IdoA thiophenyl disaccharide donors, intercepting their established utility for the assembly of both heparin- and heparan sulfate-like oligosaccharides. The [2.2.2] lactonization acts as a conformational switch to superdisarm iduronate components, reversible by lactone ring opening. In addition, the separated 2,4-diacetates also provide short access to all four anomeric and ring size isomers of l-iduronic acid methyl glycosides, including the first syntheses of the parent idofuranosides. X-ray structures are reported for a [2.2.2] iduronate lactone and examples of both methyl l-idopyranoside and novel methyl-l-idofuranoside systems.

Item Type: Article
Subjects: Q Science > QD Chemistry
Divisions: Faculty of Natural Sciences > School of Physical and Geographical Sciences
Related URLs:
Depositing User: Symplectic
Date Deposited: 26 Nov 2015 09:09
Last Modified: 07 May 2019 13:40
URI: https://eprints.keele.ac.uk/id/eprint/1228

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