Use of remote acyl groups for stereoselective 1,2-cis-glycosylation with fluorinated glucosazide thiodonors.

0525445 - ÚCHP 2021 RIV GB eng J - Článek v odborném periodiku
Hamala, Vojtěch - Červenková Šťastná, Lucie - Kurfiřt, Martin - Cuřínová, Petra - Dračínský, Martin - Karban, Jindřich
Use of remote acyl groups for stereoselective 1,2-cis-glycosylation with fluorinated glucosazide thiodonors.
Organic & Biomolecular Chemistry. Roč. 18, Č. 28 (2020), s. 5427-5434. ISSN 1477-0520. E-ISSN 1477-0539
Grant CEP: GA ČR(CZ) GA17-18203S
Institucionální podpora: RVO:67985858 ; RVO:61388963
Klíčová slova: protecting group * glycosylation * carbohydrate
Obor OECD: Organic chemistry; Organic chemistry (UOCHB-X)
Impakt faktor: 3.876, rok: 2020
Způsob publikování: Open access s časovým embargem

Fluorinated glycans are valuable probes for studying carbohydrate–protein interactions at the atomic level. Glucosamine is a ubiquitous component of glycans, and the stereoselective synthesis of α-linked fluorinated glucosamine is a challenge associated with the chemical synthesis of fluorinated glycans. We found that introducing a 6-O-acyl protecting group onto 3-fluoro and 4-fluoro glucosazide thiodonors
endowed them with moderate α-selectivity in the glycosylation of carbohydrate acceptors, which was further improved by adjusting the acceptor reactivity via O-benzoylation. Excellent stereoselectivity was achieved for 3,6-di-O-acyl-4-fluoro analogues. The glycosylation of threonine-derived acceptors enabled the stereoselective synthesis of the protected fluorinated analogue of α-GlcNAc-O-Thr, a moiety
abundant in cell-surface O-glycans of the protozoan parasite Trypanosoma cruzi. DFT calculations supported the involvement of transient cationic species which resulted from the stabilization of the oxocarbenium ion through O-6 acyl group participation.
Trvalý link: http://hdl.handle.net/11104/0309994