Synthesis of 4-thio-d-glucopyranose and interconversion to 4-thio-d-glucofuranose.

Porter, Jack; Lima, Marcelo A.; Pongener, Imlirenla; Miller, Gavin

Abstract

Sulfur containing glycosides offer an exciting prospect for inclusion within noncanonical glycan sequences, particularly as enabling probes for chemical glycobiology and for carbohydrate-based therapeutic development. In this context, we required access to 4-thio-d-glucopyranose and sought its chemical synthesis. Unable to isolate this material in homogenous form, we observed instead a thermodynamic preference for interconversion of the pyranose to 4-thio-d-glucofuranose. Accordingly, we present an improved method to access both bis(4-thio-d-glucopyranoside)-4,4'-disulfide and 4-thio-d-glucofuranose from a single precursor, demonstrating that the latter compound can be accessed from the former using a dithiothreitol controlled reduction of the disulfide. The dithiothreitol-mediated interconversion between pyranose (monomer and disulfide) and furanose forms for this thiosugar is monitored by 1H NMR spectroscopy over a 24-h period. Access to these materials will support accessing sulfur-containing mimetics of glucose and derivatives therefrom, such as sugar nucleotides.

Citation

Porter, J., Lima, M. A., Pongener, I., & Miller, G. (2023). Synthesis of 4-thio-d-glucopyranose and interconversion to 4-thio-d-glucofuranose. Carbohydrate Research, 524, Article 108759. https://doi.org/10.1016/j.carres.2023.108759

• Journal Article Type: Article
• Acceptance Date: Jan 23, 2023
• Online Publication Date: Jan 24, 2023
• Publication Date: Feb 1, 2023
• Publicly Available Date: May 30, 2023
• Journal: Carbohydrate Research
• Print ISSN: 0008-6215
• Publisher: Elsevier
• Peer Reviewed: Peer Reviewed
• Volume: 524
• Article Number: 108759
• DOI: https://doi.org/10.1016/j.carres.2023.108759
• Publisher URL: https://www.sciencedirect.com/science/article/pii/S0008621523000216?via%3Dihub
• Additional Information: © 2023 The Author(s). Published by Elsevier Ltd. This is an open access article under the CC BY license (http://creativecommons.org/licenses/by/4.0/).