Azide Solid Support for 3′-Conjugation of Oligonucleotides and Their Circularization by Click Chemistry

Abstract

A solid support bearing an azido linker was used to synthesize a 3'-azido-alkyl-oligonucleotide by phosphoramidite chemistry. The resulting oligonucleotide was either conjugated by 1,3-dipolar cycloaddition on solid support or in solution with mannose-propargyl derivative and in solution with dansyl propargyl. Besides, after introduction of an alkyne function at the 5'-end, the resulting oligonucleotide bearing both 3'-azide and 5'-alkyne functions was circularized.

Synergistic Effects of an Irreversible DNA Polymerase Inhibitor and DNA Damaging Agents on HeLa Cells

“…The successful coupling of phosphoramidite 11 with azide containing 7 , followed by in situ oxidation to the phosphate triester was consistent with previous reports in which these functional groups that could react with one another are successfully combined in oligonucleotide synthesis. 38 During the library synthesis the β-cyanoethyl and TBS groups in 12 were cleaved using Et 3 N base. Azide 12 was the last intermediate that was purified prior to library synthesis, as the amine (2) used for preparing the amides obtained via hydrogenation was used crude.…”

On the Compatibility of Azides in Phosphoramidite‐Based Couplings: Synthesis of a Novel, Convertible Azido‐Functionalized CyPLOS Analogue

“…[15][16][17][18][19][20][21][22] This aspect was first studied by Sekine et al, who concluded that nucleosides carrying azido groups cannot be adopted in phosphoramidite-based oligonucleotide synthesis because of the interfering Staudinger reaction that takes place between azides and P III derivatives. [24] In their experiment, 2-azido-2Ј-deoxyadenosine was treated with 1.5 equiv.…”

“…[19] In line with this interpretation, parallel experiments show that if both the azido and the hydroxyl functions are in the solid phase, the support-bound azides do not disturb the phosphoramidite coupling, and phosphite triester bonds are realized smoothly. [18,22] To the best of our knowledge, the concomitant presence in solution of an alcohol and an azide, both competing for the condensation with an activated phosphoramidite, was not investigated in detail. This issue was briefly reported in a recent paper, in which the conversion of a 4-azido-4-deoxy-d-galactoside into 4-deoxy-d-erythrohexos-3-ulose by reaction with a phosphoramidite reagent and tetrazole as a catalyst, was described.…”

“…Encouraged by the increasing use of azido groups as versatile chemical handles for easy synthetic access to various conjugates of multifunctional biopolymers, such as peptides [12] and oligonucleotides, [13][14][15][16][17][18][19][20][21][22] we revisited our original design so that this chemical entity could be kept on the CyPLOS backbone. Azido groups -if inserted at the extremities of the tentacles of these macrocycles -would allow post-synthetic condensation with labels that would enable the properties of these artificial ionophores to be studied.…”

Synthesis of Homo- and Heterofunctionalized Glycoclusters and Binding to Pseudomonas aeruginosa Lectins PA-IL and PA-IIL

“…and 11, 40 the phosphoramidite derivatives 4,34 15,41 and 16, 42 and the carbohydrate derivatives 2, 43 7, 44 8, 45 and 1216 were synthesized according to reported protocols.Immobilization on Azide Solid Support 1 of 1-O-Propargyl-α-D-mannopyranoside 2 by Cu(I)-Catalyzed 1,3-Dipolar Cycloaddition. An aqueous solution of 1-O-propargylmannose 2 (100 mM, 50 μL), freshly prepared aqueous solutions of CuSO 4 (100 mM, 4 μL), and sodium ascorbate (500 mM, 4 μL), water (42 μL), and MeOH (100 μL) were added to 1 μmol of azide solid support 1.…”