117841-67-5Relevant articles and documents
2-Diphenylphosphinonyl-acetyl as a Remote Directing Group for the Highly Stereoselective Synthesis of β-Glycosides
Liu, Xianglai,Lin, Yetong,Liu, Ao,Sun, Qianhui,Sun, Huiyong,Xu, Peng,Li, Guolong,Song, Yingying,Xie, Weijia,Sun, Haopeng,Yu, Biao,Li, Wei
supporting information, p. 443 - 452 (2021/12/27)
The configuration of the anomeric glycosidic linkages is crucial for maintaining the biological functions and activities of carbohydrate molecules. However, their stereochemistry control in glycosylation represents one of the most challenging tasks in car
How do Various Reaction Parameters Influence Anomeric Selectivity in Chemical Glycosylation with Thioglycosides and NIS/TfOH Activation?
Andersen, Sofie M.,Heuckendorff, Mads,Jensen, Henrik H.,Trinderup, Helle H.
, p. 3251 - 3259 (2021/06/25)
The reaction of glycosyl donor phenyl 2,3,4,6-tetra-O-benzyl-1-thio-β-D-glucopyranoside with NIS/TfOH(cat.) was systematically studied under various reaction conditions. Neither the molecular sieve pore size nor amount of NIS activator was found to have a
Visible-light-induced photoacid catalysis: Application in glycosylation with: O -glycosyl trichloroacetimidates
Li, Juncheng,Wang, Ting,Zhao, Gaoyuan
supporting information, p. 12659 - 12662 (2021/12/07)
The development of visible-light-induced photoacid catalyzed glycosylation is reported. The eosin Y and PhSSPh catalyst system is applied to realize glycosylation with different glycosyl donors upon light irradiation. The reaction shows a broad substrate
Automated Quantification of Hydroxyl Reactivities: Prediction of Glycosylation Reactions
Chang, Chun-Wei,Lin, Mei-Huei,Chan, Chieh-Kai,Su, Kuan-Yu,Wu, Chia-Hui,Lo, Wei-Chih,Lam, Sarah,Cheng, Yu-Ting,Liao, Pin-Hsuan,Wong, Chi-Huey,Wang, Cheng-Chung
supporting information, p. 12413 - 12423 (2021/05/03)
The stereoselectivity and yield in glycosylation reactions are paramount but unpredictable. We have developed a database of acceptor nucleophilic constants (Aka) to quantify the nucleophilicity of hydroxyl groups in glycosylation influenced by the steric, electronic and structural effects, providing a connection between experiments and computer algorithms. The subtle reactivity differences among the hydroxyl groups on various carbohydrate molecules can be defined by Aka, which is easily accessible by a simple and convenient automation system to assure high reproducibility and accuracy. A diverse range of glycosylation donors and acceptors with well-defined reactivity and promoters were organized and processed by the designed software program “GlycoComputer” for prediction of glycosylation reactions without involving sophisticated computational processing. The importance of Aka was further verified by random forest algorithm, and the applicability was tested by the synthesis of a Lewis A skeleton to show that the stereoselectivity and yield can be accurately estimated.
A Mechanistic Probe into 1,2-cis Glycoside Formation Catalyzed by Phenanthroline and Further Expansion of Scope
Li, Jiayi,Nguyen, Hien M.
supporting information, p. 4054 - 4066 (2021/07/16)
Phenanthroline, a rigid and planar compound with two fused pyridine rings, has been used as a powerful ligand for metals and a binding agent for DNA/RNA. We discovered that phenanthroline could be used as a nucleophilic catalyst to efficiently access high
HEPARANASE INHIBITORS FOR TREATMENT OF DIABETES
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Paragraph 0302; 0321; 0323, (2021/07/10)
Anti-heparanase compounds for the treatment of diabetes are described. The anti-heparanase compounds are high affinity, synthetic glycopolymers that result in minimal anticoagulant activity. Stereoselective fluorinated forms of these compounds are also pr
A "traceless" Directing Group Enables Catalytic SN2 Glycosylation toward 1,2- cis-Glycopyranosides
Fu, Yue,Liu, Peng,Ma, Xu,Zhang, Liming,Zheng, Zhitong,Zhu, Xijun
supporting information, p. 11908 - 11913 (2021/08/20)
Generally applicable and stereoselective formation of 1,2-cis-glycopyranosidic linkage remains a long sought after yet unmet goal in carbohydrate chemistry. This work advances a strategy to this challenge via stereoinversion at the anomeric position of 1,2-trans glycosyl ester donors. This SN2 glycosylation is enabled under gold catalysis by an oxazole-based directing group optimally tethered to a leaving group and achieved under mild catalytic conditions, in mostly excellent yields, and with good to outstanding selectivities. The strategy is also applied to the synthesis of oligosaccharides.
Solvent-free, under air selective synthesis of α-glycosides adopting glycosyl chlorides as donors
Bedini, Emiliano,Iadonisi, Alfonso,Traboni, Serena,Vessella, Giulia
, p. 5157 - 5163 (2020/07/23)
α-Glycosides are highly relevant synthetic targets due to their abundance in natural oligosaccharides involved in many biological processes. Nevertheless their preparation is hampered by several issues, due to both the strictly anhydrous conditions typically required in glycosylation procedures and the non-trivial achievement of high α-stereoselectivity, one of the major challenges in oligosaccharide synthesis. In this paper we report a novel and efficient approach for the highly stereoselective synthesis of α-glycosides. This is based on the unprecedented solvent-free combination of triethylphosphite, tetrabutylammonium bromide and N,N-diisopropylethylamine for the activation of glycosyl chlorides under air. Despite the relative stability of glycosyl chlorides with respect to more reactive halide donors, the solvent-free procedure allowed a wide set of α-glycosides, including biorelevant fragments, to be obtained in much shorter times compared with similar glycosylation approaches in solution. The presented method features a wide target scope and functional group compatibility, also serving with partially disarmed substrates, and it does not require a high stoichiometric excess of reagents nor the preparation of expensive precursors. The solvent-free glycosylation can be even directly performed from 1-hydroxy sugars without purification of the in situ generated chloride, providing an especially useful opportunity in the case of highly reactive and labile glycosyl donors. This journal is
Cyanomethyl Ether as an Orthogonal Participating Group for Stereoselective Synthesis of 1,2-trans-β-O-Glycosides
Molla, Mosidur Rahaman,Das, Pradip,Guleria, Kanika,Subramanian, Ranga,Kumar, Amit,Thakur, Rima
, p. 9955 - 9968 (2020/09/09)
Stereoselective formation of glycosidic linkages has been the prime focus for contemporary carbohydrate chemistry. Herein, we report cyanomethyl (CNMe) ether as an efficient and effective participating orthogonal protecting group for the stereoselective synthesis of 1,2-trans-β-O-glycosides. The participating group facilitated good to high β-selective glycosylation with a broad range of electron-rich and electron-deficient glycosyl acceptors. Detailed experimental and theoretical studies reveal the involvement of CNMe ether in the formation of a six-membered imine-type cyclic intermediate for the observed stereoselectivity. Rapid incorporation and selective removal of the CNMe ether group in the presence of benzyl ether and isopropylidene acetal protection have also been reported here. The nitrile group provided an opportunity for the glycodiversification through further derivatizations.
A visible light promoted O-glycosylation with glycosyl trichloroacetimidates using eosin Y as an organo photoacid
Li, Hongfang,Liu, Jiao,Ni, Guanghui,Wang, Haimei,Yin, Shan
, (2020/03/06)
A photoacid catalyzed O-glycosylation of alcohols with glycosyl trichloroacetimidates in the presence of commercially available phenolic photoacids, fluorescein, 4′,5′-dibromo-fluorescein, and eosin Y under visible light irradiation by blue LEDs was devel
