3180-76-5Relevant articles and documents
NIS/TMSOTf-Promoted Glycosidation of Glycosyl ortho-Hexynylbenzoates for Versatile Synthesis of O-Glycosides and Nucleosides
Liu, Rongkun,Hua, Qingting,Lou, Qixin,Wang, Jiazhe,Li, Xiaona,Ma, Zhi,Yang, You
, p. 4763 - 4778 (2021/04/06)
Glycosidation plays a pivotal role in the synthesis of O-glycosides and nucleosides that mediate a diverse range of biological processes. However, efficient glycosidation approach for the synthesis of both O-glycosides and nucleosides remains challenging in terms of glycosidation yields, mild reaction conditions, readily available glycosyl donors, and cheap promoters. Here, we report a versatile N-iodosuccinimide/trimethylsilyl triflate (NIS/TMSOTf)-promoted glycosidation approach with glycosyl ortho-hexynylbenzoates as donors for the highly efficient synthesis of O-glycosides and nucleosides. The glycosidation approach highlights the merits of mild reaction conditions, cheap promoters, extremely wide substrate scope, and good to excellent yields. Notably, the glycosidation approach performs very well in the construction of a series of challenging O- and N-glycosidic linkages. The glycosidation approach is then applied to the efficient synthesis of oligosaccharides via the one-pot strategy and the stepwise strategy. On the basis of the isolation and characterization of the departure species derived from the leaving group, a plausible mechanism of NIS/TMSOTf-promoted glycosidation of glycosyl ortho-hexynylbenzoates is proposed.
Inhibition of tyrosyl-DNA phosphodiesterase 1 by lipophilic pyrimidine nucleosides
Chernyshova, Irina A.,Drenichev, Mikhail S.,Dyrkheeva, Nadezhda S.,Ilina, Ekaterina S.,Ivanov, Georgy A.,Lavrik, Olga I.,Mikhailov, Sergey N.,Oslovsky, Vladimir E.,Zakharenko, Alexandra L.
supporting information, (2020/09/17)
Inhibition of DNA repair enzymes tyrosyl-DNA phosphodiesterase 1 and poly(ADP-ribose) polymerases 1 and 2 in the presence of pyrimidine nucleoside derivatives was studied here. New effective Tdp1 inhibitors were found in a series of nucleoside derivatives possessing 2′,3′,5′-tri-O-benzoyl-d-ribofuranose and 5-substituted uracil moieties and have half-maximal inhibitory concentrations (IC50) in the lower micromolar and submicromolar range. 2′,3′,5′-Tri-Obenzoyl- 5-iodouridinemanifested the strongest inhibitory effect on Tdp1 (IC50 = 0.6 μM). Adecrease in the number of benzoic acid residues led to a marked decline in the inhibitory activity, and pyrimidine nucleosides lacking lipophilic groups (uridine, 5-fluorouridine, 5-chlorouridine, 5-bromouridine, 5-iodouridine, and ribothymidine) did not cause noticeable inhibition of Tdp1 (IC50 > 50 μM). No PARP1/2 inhibitors were found among the studied compounds (residual activity in the presence of 1mMsubstances was 50-100%). Several O-benzoylated uridine and cytidine derivatives strengthened the action of topotecan on HeLa cervical cancer cells.
Ortho-(1-phenylvinyl)benzoate glycosylation donor, and preparation method and application thereof
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Paragraph 0193; 0197-0201, (2020/05/01)
The invention discloses an ortho-(1-phenylvinyl)benzoate glycosylation donor, and a preparation method and an application thereof in a glycosylation reaction. The ortho-(1-phenylvinyl)benzoate glycosylation donor is stable, is easy to prepare and store, and is widely applied to the construction of various oxygen glucosides and nucleoside (nitrogen glucoside) glycosidic bonds. The leaving group ofthe donor is an alkenyl ester, has a high activity, and can be combined with thioglycoside or n-pentenyl ether glucoside through a one-pot glycosylation reaction to synthesize oligosaccharide. The glycosylation reaction conditions are mild, and receptors sensitive to acid and electrophilic reagents can tolerate the glycosylation reaction conditions.
Larger laboratory scale synthesis of 5-methyluridine and formal synthesis of its L-enantiomer
Thiesen, Luciano J. Hoeltgebaum,Cabral, Nadia,Joselice E Silva, Maria,Bezerra, Gilson,Doboszewski, Bogdan
, p. 249 - 264 (2017/06/19)
A larger laboratory scale synthesis (>60 g per run) of 5-methyluridine is presented. The critical intermediate 1,2-O-isopropylidene-α-D-ribofuranose was prepared from very cheap D-glucose via D-allose. Its L-enantiomer was obtained from L-arabinose via L-glucose, and also from L-xylose. {figure presented}.
A solid-supported acidic oxazolium perchlorate as an easy-handling catalyst for the synthesis of modified pyrimidine nucleosides via Vorbrüggen-type N-glycosylation
Basu, Nabamita,Oyama, Kin-ichi,Tsukamoto, Masaki
supporting information, p. 1921 - 1924 (2017/04/27)
A solid-supported acidic oxazolium perchlorate was investigated as a heterogeneous catalyst in N-glycosylation reactions using silylated modified pyrimidines and an acylated ribose or glucose to afford the corresponding pyrimidine nucleosides. This salt is a nonhygroscopic and stable powder whose activity is comparable to that of 2-methyl-5-phenylbenzoxazolium perchlorate. A reaction with this polymer catalyst can be conducted on a gram scale. Reusability of the solid-supported catalyst was also investigated.
A general method for N-glycosylation of nucleobases promoted by (p-Tol)2SO/Tf2O with thioglycoside as donor
Liu, Guang-Jian,Zhang, Xiao-Tai,Xing, Guo-Wen
supporting information, p. 12803 - 12806 (2015/08/06)
Based on a preactivation strategy using the (p-Tol)2SO/Tf2O system, a series of nucleosides were synthesized by coupling various thioglycosides with pyrimidines and purines under mild conditions. High yields and excellent β-stereoselectivities were obtained with either armed or disarmed N-glycosylation donors by tuning the amount of (p-Tol)2SO additive.
Propargyl 1,2-orthoesters for a catalytic and stereoselective synthesis of pyrimidine nucleosides
Rao, Boddu Venkateswara,Manmode, Sujit,Hotha, Srinivas
, p. 1499 - 1505 (2015/02/19)
Pyrimidine nucleosides are synthesized by using propargyl 1,2-orthoesters and Au(III) salt as a catalyst. Strategically positioned 1,2-orthoesters are found to yield only 1,2-trans nucleosides and enable preparation of 2′-OH containing pyrimidine nucleosides. The glycosyl donor employed in this study is stable and easily accessible. The identified high-yielding protocol is mild, diastereoselective, and catalytic.
Antifreeze protein-induced selective crystallization of a new thermodynamically and kinetically less preferred molecular crystal
Wang, Sen,Wen, Xin,Golen, James A.,Arifin, Josh F.,Rheingold, Arnold L.
, p. 16104 - 16112 (2014/04/03)
The formation of a new, dihydrate crystalline form of 5-methyluridine (m5U) was selectively induced by a protein additive, antifreeze protein (AFP) in a highly efficient manner (in 10-6molar scale, whereas known kinetic additives nee
A Reverse Strategy for synthesis of nucleosides based on n-pentenyl orthoester donors
Fraser-Reid, Bert,Ganney, Parimala,Ramamurty, Changalvala V. S.,Gomez, Ana M.,Lopez, J. Cristobal
supporting information, p. 3251 - 3253 (2013/05/08)
Strategically derivatized NPOE glycosyl donors, are able to efficiently glycosylate silylated nucleobases under mild conditions, even as low as -78°C if necessary. Ensuring trans-1,2 glycosylation, thus permitting, unlike classical procedures, a Reverse Strategy for the synthesis of ribonucleosides, where glycosylation occurs late, rather than early, and convergency is optimized.
An economical synthesis of D- and L-pyrimidine arabinoand ribonucleosides
Lazrek, Hassan B.,Ouzebla, Driss,Faraj, Abdesslem
experimental part, p. 227 - 234 (2012/04/18)
The one-step synthesis of several β-D/L-arabino- and ribonucleosides was performed in good yields under reflux or microwave-assisted fusion method. A comparison of the two methods showed that better yields were obtained using the reflux conditions. Copyright Taylor and Francis Group, LLC.
