title: Stereocontrolled 1-S-glycosylation and comparative binding studies of photoprobe-thiosaccharide conjugates with theirO-linked analogs.
abstract: The use of thioglycosides and other glycan derivatives with anomeric sulfur linkages is gaining increasing interest, both in synthesis and in various biological contexts. Herein, we demonstrate the occurrence and circumvention of anomerization during 1-S-glycosylation reactions, and present highly efficient and stereocontrolled syntheses of a series of photoprobe-thiosaccharide conjugates. Mutarotation of glycosyl thiols proved to be the origin of the anomeric mixtures formed, and kinetic effects could be used to circumvent anomerization. The synthesized carbohydrate conjugates were then evaluated by both solution- and solid-phase-based techniques. Both binding results showed that theS-linked glyco-sides interact with their cognate lectins comparably to the correspondingO-analogs in the present cases, thus demonstrating the reliability of the solid-support platform built upon our photo-initiated carbohydrate immobilization method for probing protein bindings, and showing the potential of combining these two means for studying carbohydrate-protein interactions.
authors.affiliation: Department of Chemistry, Royal Institute of Technology (KTH), Teknikringen 30, S-10044, Stockholm, Sweden.
authors.forename: Lingquan
authors.initials: L
authors.lastname: Deng
authors.affiliation: Department of Chemistry, University of Massachusetts Lowell, 1 University Ave., Lowell, MA 01854, USA.
authors.forename: Xin
authors.initials: X
authors.lastname: Wang
authors.affiliation: Department of Chemistry, University of Massachusetts Lowell, 1 University Ave., Lowell, MA 01854, USA.
authors.forename: Suji
authors.initials: S
authors.lastname: Uppalapati
authors.affiliation: Department of Chemistry, Royal Institute of Technology (KTH), Teknikringen 30, S-10044, Stockholm, Sweden.
authors.forename: Oscar
authors.initials: O
authors.lastname: Norberg
authors.affiliation: Department of Chemistry, Royal Institute of Technology (KTH), Teknikringen 30, S-10044, Stockholm, Sweden ; School of Chemistry and Chemical Engineering, Huazhong University of Science and Technology, Luoyu Rd. 1037, Wuhan, China.
authors.forename: Hai
authors.initials: H
authors.lastname: Dong
authors.affiliation: Department of Chemistry, Royal Institute of Technology (KTH), Teknikringen 30, S-10044, Stockholm, Sweden.
authors.forename: Adrien
authors.initials: A
authors.lastname: Joliton
authors.affiliation: Department of Chemistry, Royal Institute of Technology (KTH), Teknikringen 30, S-10044, Stockholm, Sweden ; Department of Chemistry, University of Massachusetts Lowell, 1 University Ave., Lowell, MA 01854, USA.
authors.forename: Mingdi
authors.initials: M
authors.lastname: Yan
authors.affiliation: Department of Chemistry, Royal Institute of Technology (KTH), Teknikringen 30, S-10044, Stockholm, Sweden.
authors.forename: Olof
authors.initials: O
authors.lastname: Ramström
keywords: carbohydrates; organic materials; organic synthesis; photochemistry; protein interactions; stereocontrol