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

Kód výsledku v IS VaVaI

<a href="https://www.isvavai.cz/riv?ss=detail&h=RIV%2F61388963%3A_____%2F20%3A00525445" target="_blank" >RIV/61388963:_____/20:00525445 - isvavai.cz</a>

Nalezeny alternativní kódy

RIV/67985858:_____/20:00525445 RIV/60461373:22310/20:43923766 RIV/60461373:22810/20:43923766

Výsledek na webu

<a href="http://hdl.handle.net/11104/0309994" target="_blank" >http://hdl.handle.net/11104/0309994</a>

DOI - Digital Object Identifier

<a href="http://dx.doi.org/10.1039/d0ob01065k" target="_blank" >10.1039/d0ob01065k</a>

Jazyk výsledku

angličtina

Název v původním jazyce

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

Popis výsledku v původním jazyce

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 thiodonorsnendowed 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 moietynabundant 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.

Název v anglickém jazyce

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

Popis výsledku anglicky

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 thiodonorsnendowed 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 moietynabundant 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.

Druh

J_imp - Článek v periodiku v databázi Web of Science

CEP obor

—

OECD FORD obor

10401 - Organic chemistry

Projekt

<a href="/cs/project/GA17-18203S" target="_blank" >GA17-18203S: Stereodirektivní efekty zavedení fluoru do poloh C-3 a C-4 2-azido-2-deoxy-hexopyranosových donorů</a><br>

Návaznosti

I - Institucionalni podpora na dlouhodoby koncepcni rozvoj vyzkumne organizace

Rok uplatnění

2020

Kód důvěrnosti údajů

S - Úplné a pravdivé údaje o projektu nepodléhají ochraně podle zvláštních právních předpisů

Název periodika

Organic & Biomolecular Chemistry

ISSN

1477-0520

e-ISSN

—

Svazek periodika

18

Číslo periodika v rámci svazku

28

Stát vydavatele periodika

GB - Spojené království Velké Británie a Severního Irska

Počet stran výsledku

8

Strana od-do

5427-5434

Kód UT WoS článku

000550965600015

EID výsledku v databázi Scopus

2-s2.0-85088430731