title: Mechanistic Investigations into the Application of Sulfoxides in Carbohydrate Synthesis.
abstract: The utility of sulfoxides in a diverse range of transformations in the field of carbohydrate chemistry has seen rapid growth since the first introduction of a sulfoxide as a glycosyl donor in 1989. Sulfoxides have since developed into more than just anomeric leaving groups, and today have multiple roles in glycosylation reactions. These include as activators for thioglycosides, hemiacetals, and glycals, and as precursors to glycosyl triflates, which are essential for stereoselective β-mannoside synthesis, and bicyclic sulfonium ions that facilitate the stereoselective synthesis of α-glycosides. In this review we highlight the mechanistic investigations undertaken in this area, often outlining strategies employed to differentiate between multiple proposed reaction pathways, and how the conclusions of these investigations have and continue to inform upon the development of more efficient transformations in sulfoxide-based carbohydrate synthesis.
authors.affiliation: York Structural Biology Lab, Department of Chemistry, University of York, Heslington Road, York, YO10 5DD, UK. martin.fascione@york.ac.uk.
authors.forename: Martin A
authors.identifier: http://orcid.org/0000-0002-0066-4419
authors.initials: MA
authors.lastname: Fascione
authors.affiliation: York Structural Biology Lab, Department of Chemistry, University of York, Heslington Road, York, YO10 5DD, UK.
authors.forename: Robin
authors.initials: R
authors.lastname: Brabham
authors.affiliation: School of Chemistry and Astbury Centre for Structural Molecular Biology, University of Leeds, Woodhouse Lane, Leeds, LS2 9JT, UK. w.b.turnbull@leeds.ac.uk.
authors.forename: W Bruce
authors.initials: WB
authors.lastname: Turnbull
mesh_terms: D002241:Carbohydrates / Q000138:chemical synthesis* / Q000737:chemistry; D006031:Glycosylation; D008362:Mannosides / Q000138:chemical synthesis / Q000737:chemistry; D013454:Sulfoxides / Q000737:chemistry*; D013865:Thioglycosides / Q000737:chemistry
chemical_list: D002241:Carbohydrates; D008362:Mannosides; D013454:Sulfoxides; D013865:Thioglycosides
keywords: carbohydrates; glycosylation; mechanism; organic synthesis; sulfoxides