title: Intramolecular thiol-yne cyclisation as a novel strategy for thioglycal synthesis.
abstract: A novel intramolecular thiol-yne cyclisation strategy has been developed for the synthesis of thioglycals. Both ionic and radical mediated cyclisation pathways have been investigated for D- and L-sugars. The ionic cyclisation provides exclusive access to 5-exo products directly from the thioesters whereas the radical cyclisation provides access to both 5-exo and 6-endo products upon photochemical irradiation of the free thiols. These are the first examples of intramolecular thiol-yne cyclisation reactions applied to thiosugar synthesis.
authors.affiliation: School of Chemistry, Trinity Biomedical Sciences Institute, Trinity College, 152-160 Pearse Street, Dublin 2, Ireland. eoin.scanlan@tcd.ie.
authors.forename: Vincent
authors.initials: V
authors.lastname: Corcé
authors.forename: Lauren
authors.initials: L
authors.lastname: McSweeney
authors.forename: Aoife
authors.initials: A
authors.lastname: Malone
authors.forename: Eoin M
authors.initials: EM
authors.lastname: Scanlan
mesh_terms: D000480:Alkynes / Q000737:chemistry*; D003500:Cyclization; D006027:Glycosides / Q000138:chemical synthesis* / Q000737:chemistry; D008968:Molecular Conformation; D013438:Sulfhydryl Compounds / Q000737:chemistry*
chemical_list: D000480:Alkynes; D006027:Glycosides; D013438:Sulfhydryl Compounds