title: On the stereoselectivity of glycosidation of thiocyanates, thioimidates, and thioglycosides.
abstract: Comparative side-by-side glycosylation studies demonstrated that glycosyl thiocyanates, thioimidates, and thioglycosides provide comparative stereoselectivities in glycosylations. Very high α-stereoselectivity that was previously recorded for glycosyl thiocyanates can be achieved, but only if glycosyl acceptors are equipped with electron-withdrawing acyl substituents. Partially benzylated glycosyl acceptors provided relatively modest stereoselectivity, which was on a par with other common glycosyl donors. Accordingly, thioimidates and thioglycosides showed high stereoselectivity similarly to that of thiocyanates with different classes of acylated primary and secondary glycosyl acceptors.
authors.affiliation: Department of Chemistry and Biochemistry, University of Missouri - St. Louis, One University Boulevard, St. Louis, MO 63121, USA.
authors.forename: Sophon
authors.initials: S
authors.lastname: Kaeothip
authors.forename: Steven J
authors.initials: SJ
authors.lastname: Akins
authors.forename: Alexei V
authors.initials: AV
authors.lastname: Demchenko
mesh_terms: D006031:Glycosylation; D007096:Imidoesters / Q000737:chemistry*; D015394:Molecular Structure; D013237:Stereoisomerism; D013861:Thiocyanates / Q000737:chemistry*; D013865:Thioglycosides / Q000737:chemistry*
chemical_list: D007096:Imidoesters; D013861:Thiocyanates; D013865:Thioglycosides