175978-41-3Relevant academic research and scientific papers
Linear Synthesis of De novo Oligo-Iduronic Acid
Shanthamurthy, Chethan D.,Kikkeri, Raghavendra
, p. 2950 - 2953 (2019)
L-Iduronic acid (IdoA) plays a pivotal role in glycosaminoglycan (GAG) protein interactions. However, the structural microheterogeneity of GAG appears to impede the systematic investigation of IdoA functions. Under such conditions, oligo-Iduronic acid (Oligo-IdoA) are ideal and straightforward heparin mimetics to unravel the relationship between IdoA structure and functions. Herein, we report for the first-time linear synthesis of rare oligo-IdoA precursor utilizing anhydrous β-L-idopyranosyl and IdoA thiophenol building block. After screening various synthetic strategies, we have Installed successive IdoA by 5 step reactions with 25–26 % overall yield. These oligo-IdoA are expected to be excellent probes to understand conformational plasticity of IdoA and fine tune carbohydrate–protein interactions.
Glycosylations of Simple Acceptors with 2-O-Acyl l-Idose or l-Iduronic Acid Donors Reveal Only a Minor Role for Neighbouring-Group Participation
Mohamed, Shifaza,He, Qi Qi,Lepage, Romain J.,Krenske, Elizabeth H.,Ferro, Vito
, p. 2214 - 2227 (2018/06/04)
Several l-idose and l-iduronic acid glycosyl donors (mostly thioglycosides but also halides and trichloroacetimidates) with acyl protecting groups at the C-2 position were prepared and evaluated in glycosylation reactions with simple acceptors. In glycosaminoglycan oligosaccharide syntheses in the literature, the presence of C-2 acyl protecting groups in l-ido-configured glycosyl donors generally results in exclusive formation of 1,2-trans glycosidic linkages, a finding that has typically been attributed to neighbouring-group participation. However, glycosylations of simple alcohols with l-ido-configured donors (particularly thioglycosides), reported here, generally displayed incomplete stereocontrol and gave mixtures of the 1,2-trans and 1,2-cis products, suggesting that neighbouring-group participation has lesser importance in these reactions. Glycosyl donors and reaction conditions were identified that gave improved, but not exclusive, selectivity for the desired α-l-anomer (1,2-trans) as the major product. Interestingly, glycosylations under the same reaction conditions with more complex monosaccharide acceptors gave exclusively the expected 1,2-trans products. The role of neighbouring-group participation in these glycosylations was explored with density functional theory (DFT) calculations, which revealed that the non-stereoselective addition of the acceptor alcohol to the intermediate oxocarbenium ion is competitive with the stereospecific addition of the acceptor to the acyloxonium ion intermediate.
Total synthesis of anticoagulant pentasaccharide fondaparinux
Li, Tiehai,Ye, Hui,Cao, Xuefeng,Wang, Jiajia,Liu, Yonghui,Zhou, Lifei,Liu, Qiang,Wang, Wenjun,Shen, Jie,Zhao, Wei,Wang, Peng
, p. 1071 - 1080 (2014/05/20)
The anticoagulant pentasaccharide fondaparinux was synthesized using an improved and optimized synthetic strategy including a convergent [3+2] coupling approach, orthogonal protecting groups and various glycosyl donors. The new methods of glycosylation were also used for controlling the stereochemical configuration and improving the yield of the glycosylation. In addition, HPLC and NMR methods to monitor the process of total synthesis of fondaparinux were employed. This work provides a comprehensive elaboration for the synthesis and analysis of fondaparinux based on related literature, as well as abundant information for the synthesis of heparin-like oligosaccharides. A matter of protection! The anticoagulant pentasaccharide fondaparinux was synthesized using an improved and optimized synthetic strategy. The process of total synthesis was monitored by HPLC and NMR. This work will contribute to continued improvement of the multistep production of fondaparinux and provide abundant information for the synthesis of heparin-like oligosaccharides.
Toward the solid-phase synthesis of heparan sulfate oligosaccharides: Evaluation of iduronic acid and idose building blocks
Guedes, Nerea,Czechura, Pawel,Echeverria, Begona,Ruiz, Ada,Michelena, Olatz,Martin-Lomas, Manuel,Reichardt, Niels-Christian
, p. 6911 - 6934 (2013/08/23)
Glycan arrays have been established as the premier technical platform for assessing the specificity of carbohydrate binding proteins, an important step in functional glycomics research. Access to large libraries of well-characterized oligosaccharides rema
A modular strategy toward the synthesis of heparin-like oligosaccharides using monomeric building blocks in a sequential glycosylation strategy
Codee, Jeroen D. C.,Stubba, Bas,Schiattarella, Marialuisa,Overkleeft, Herman S.,Van Boeckel, Constant A. A.,Van Boom, Jacques H.,Van Der Marel, Gijsbert A.
, p. 3767 - 3773 (2007/10/03)
A novel flexible assembly strategy is described for the modular synthesis of heparin and heparan sulfates. The reported strategy uses monomeric building bocks to construct the oligosaccharide chain to attain a maximum degree of flexibility. In the assembly, 1-hydroxyl glucosazido- and 1-thio uronic acid donors are combined in a sequential glycosylation protocol using sulfonium triflate activator systems. The key 1-thio uronic acids were obtained in an efficient manner from diacetone glucose employing a chemo- and regioselective oxidation of partially protected glucose and idose thioglycosides.
L-Iduronic acid derivatives as glycosyl donors
Tabeur, Christine,Machetto, Francoise,Mallet, Jean-Maurice,Duchaussoy, Philippe,Petitou, Maurice,Sinay, Pierre
, p. 253 - 276 (2007/10/03)
O-[Methyl (2-O-acetyl-3-O-benzyl-4-O-levulinyl-α, and β-L-idopyranosid)uronate]trichloroacetimidate and the corresponding n-pentenyl glycosides are efficient L-iduronic acid glycosyl donors. Both have been used for the high-yielding synthesis of basic disaccharide blocks which are useful for the subsequent synthesis of complex oligosaccharides related to heparin/heparan sulfate, and dermatan sulfate. In contrast, the corresponding thioethyl glycosides, thiophenyl glycosides, and fluoride, did not yield the expected disaccharides.
