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Synlett 2019; 30(19): 2185-2192
DOI: 10.1055/s-0039-1690710
letter
© Georg Thieme Verlag Stuttgart · New York

Preparation of α-l-Rhamnobiosides by Open and Conventional Glycosylations for Studies of the rHPL Lectin

Fruzsina Demeter
a   Department of Pharmaceutical Chemistry, University of Debrecen, Egyetem tér 1, 4032 Debrecen, Hungary   eMail: herczeg.mihaly@science.unideb.hu
b   MTA-DE Molecular Recognition and Interaction Research Group, University of Debrecen, Egyetem tér 1, 4032 Debrecen, Hungary
c   Doctoral School of Chemistry, University of Debrecen, Egyetem tér 1, 4032 Debrecen, Hungary
,
Tímea Balogh
a   Department of Pharmaceutical Chemistry, University of Debrecen, Egyetem tér 1, 4032 Debrecen, Hungary   eMail: herczeg.mihaly@science.unideb.hu
,
Tse-Kai Fu
d   Institute of Molecular and Cellular Biology, National Tsing Hua University, Hsinchu, Taiwan, R. of China
,
Margaret Dah-Tsyr Chang
d   Institute of Molecular and Cellular Biology, National Tsing Hua University, Hsinchu, Taiwan, R. of China
e   Molecular Infectious Disease Research Center, Chang Gung Memorial Hospital, Chang Gung University College of Medicine, Taoyuan, Taiwan, R. of China
,
Yuan-Chuan Lee
d   Institute of Molecular and Cellular Biology, National Tsing Hua University, Hsinchu, Taiwan, R. of China
f   Department of Biology, Johns Hopkins University, Baltimore, MD 21218, USA
,
Anikó Borbás∗
a   Department of Pharmaceutical Chemistry, University of Debrecen, Egyetem tér 1, 4032 Debrecen, Hungary   eMail: herczeg.mihaly@science.unideb.hu
,
Mihály Herczeg∗
a   Department of Pharmaceutical Chemistry, University of Debrecen, Egyetem tér 1, 4032 Debrecen, Hungary   eMail: herczeg.mihaly@science.unideb.hu
g   Research Group for Oligosaccharide Chemistry of HAS, University of Debrecen, Egyetem tér 1, 4032 Debrecen, Hungary
› InstitutsangabenThis research was supported by the ÚNKP-19-3/4 New National Excellence Program of the Ministry of Human Capacities, Ministry of Science and Technology (MOST, Grant No. MOST 107-0210-01-19-04), and Industrial Value Creation Program for Academia (Grant No. 108B7016V1), Program for Translational Innovation of Biopharmaceutical Development-Technology Supporting Platform Axis (Grant No. AS-KPQ-108-TSPA). The authors gratefully acknowledge financial support for this research from the Premium Postdoctoral Program of HAS (Grant No. PPD 461038) from the National Research, Development and Innovation Office of Hungary (Grant No. K 128368) and from the EU and co-financed by the European Regional Development Fund under the project GINOP-2.3.2-15-2016-00008 and GINOP-2.3.3-15-2016-00004.
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Publikationsverlauf

Received: 31. Juli 2019

Accepted after revision: 25. September 2019

Publikationsdatum:
10. Oktober 2019 (online)

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Abstract

To study the effect of oligosaccharides on biological systems (e.g., carbohydrate–lectin interactions), chemical synthesis of the desired carbohydrate derivatives is highly desirable, but it is usually a very complicated task. Most of the stereo- and regioselective glycosylation reactions are carried out by using protected acceptors and donors. At the same time, open glycosylation (use of an unprotected acceptor) may shorten the reaction pathway, if sufficient selectivity can be achieved between the acceptor hydroxyl groups. Toward synthesis of higher oligomers and multivalent derivatives, which are often useful for lectin binding studies, open glycosylation reactions of propargyl and phenylthio rhamnosides were investigated as a rapid route to the α-(1,3)-linked rhamnobioside binding motif. The efficacy of open glycosylations proved to be highly dependent on both the type of donor and the solvent applied. Using a trichloroacetimidate donor in 1,4-dioxane, the open glycosylation reactions proceeded with high regioselectivity and in good yields. Conventional glycosylations, on the other hand, afforded the α-(1,2)- and α-(1,3)-linked rhamnobioside derivatives with slightly higher yields via three-step longer syntheses.

Key words

rhamnobioside - trichloroacetimidate - thioglycoside - regioselective - stereoselective - glycosylation

Supporting Information

    Supporting information for this article is available online at https://doi.org/10.1055/s-0039-1690710.
  • Supporting Information
 

  • References and Notes

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