Efficient syntheses of artificial nucleases containing mono-, di- and tri-[12]aneN3 ligating units through click chemistry

Zan, Ju; Hao, Yan; Guo, Zhi-Fo; Lu, Zhong‐Lin

doi:10.1016/j.inoche.2010.06.009

Cited by 7 publications

(2 citation statements)

References 26 publications

(43 reference statements)

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“…In the 1 H-NMR spectra, the protons from methylene groups of [12]aneN 3 backbone appear around 1.60, 2.50, and 2.80 ppm as multiplets, which are consistent with those reported in the literatures. 29 The N-methyl groups on the [12]aneN 3 unit appear as singlet at 2.06 and 2.25 ppm for ligand 8 and 9, respectively. 24…”

Section: Synthesis Of Ligands 8 Andmentioning

confidence: 99%

Steric effects on the catalytic activities of zinc(ii) complexes containing [12]aneN3 ligating units in the cleavage of the RNA and DNA model phosphates

et al. 2012

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A series of N-methylated mono- and di-[12]aneN(3) ligands () have been synthesized and characterized. The steric effects on the catalytic activities of their mononuclear and dinuclear zinc(ii) complexes in the cleavage of a RNA model 2-hydroxypropyl 4-nitrophenyl phosphate (HPNPP, ) and a DNA model methyl 4-nitrophenyl phosphates (MPNPP, 4) in methanol have been investigated at 25 °C. In the cleavage of phosphate catalyzed by the mononuclear complexes, derived from the N-methylation in the [12]aneN(3) backbone, the plots of k(obs)versus [Zn(II)] changed from an upward curvature to linearity with increasing level of methylation, indicating that N-methylations led to a reduction of dinuclear association that was responsible for the synergetic effect. Compared to the activities of the complex with non-methylated di-[12]aneN(3) ligand, those of the dinuclear zinc(ii) complex (Zn(2)-8), which has the two N-methyl groups, were reduced by two orders of magnitude as measured by the second-order rate constants and synergetic effect in the cleavage of both model compounds. For reactions catalyzed by the fully N-methylated dinuclear complex (Zn(2)-9), no synergetic effect was observed. Nevertheless, complex Zn(2)-8 still showed the remarkable catalytic efficiency, with rate accelerations of 10(9-10)-fold in the cleavage of each of the two phosphates relative to the background reactions, and the synergetic effects of up to 561 folds. pH jump experiments confirmed that the rate-limiting step in the cleavage of by Zn(2)-8 involved the binding process, while that in the reaction with 4 was the chemical cleavage of the P-O bond. Steric effects in the cleavage reactions were analyzed in detail and were compared with the electronic effect caused by oxy anion bridging group in the di-[12]aneN(3) ligand and also with the hydrophobic effect observed in other systems. The work has further confirmed that the combination of the cooperativity between two metal ions and a medium effect could result in excellent catalytic activities for the cleavage of phosphate diesters.

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Section: Synthesis Of Ligands 8 Andmentioning

confidence: 99%

Steric effects on the catalytic activities of zinc(ii) complexes containing [12]aneN3 ligating units in the cleavage of the RNA and DNA model phosphates

et al. 2012

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“…The protons from the methylene groups of the [12]aneN 3 units generally appear around 2.20, 3.10 and 3.30 ppm as multiplets, and are consistent with those reported in the literature. 16,22,23 The synthesis of ligands 4-6 began with the alkylation reactions between the [12]aneN 3 precursor 13 and either 1,3bis(bromomethyl)benzene 10b or 5-substituted-1,3-bis-(bromomethyl)benzenes 10d/10f. Depending on the following workup procedure, the intermediates 12b/d/f were converted to nonmethyl, dimethyl, and tetramethyl substituted compounds 4b/d/f, 5b, and 6b.…”

Section: Syntheses and Characterization Of Ligands 1-6mentioning

confidence: 99%

Synthesis of mono- and di-[12]aneN3 ligands and study on the catalytic cleavage of RNA model 2-hydroxypropyl-p-nitrophenyl phosphate with their metal complexes

Guo

Hao

et al. 2011

Org. Biomol. Chem.

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A series of mono- and di-[12]aneN(3) ligands 1-6, which contain different substituents on the coordinating backbone, different linkers between two [12]aneN(3) units and different N-methylation on the [12]aneN(3) units, have been synthesized and fully characterized. The catalytic activities of their metal complexes on the cleavage of RNA model phosphate 2-hydroxypropyl-p-nitrophenyl phosphate (HPNPP) varied with the structures of the ligands and metal ions. Click reactions afforded an efficient method to prepare a series of [12]aneN(3) ligands, however, the incorporation of triazole moieties reduced the catalytic activities due to their coordination with metal ions and the strong inhibition from the triflate counter ion. Dinuclear zinc(II) complexes containing an m-xylyl bridge showed higher catalytic activities with synergistic effects up to 700-fold. Copper(II) complexes with the ligands without triazole moieties proved to be highly reactive and showed strong cooperativity between the two copper(II) ions. In terms of k(2), dinuclear complexes Zn(2)-3b, Zn(2)-3d, Zn(2)-4b, and Cu(2)-4b afforded activities of 7.9 × 10(5), 3.9 × 10(4), 9.0 × 10(4), and 8.1 × 10(4)-fold higher than that of methoxide. The ortho arrangement of the two [12]aneN(3) units and the presence of 5- or 2-positioned substituents in the benzene ring as well as N-methylation of [12]aneN(3) units greatly reduced the catalytic activities due to the steric effects. These results clearly indicate that the structures of the linker between two [12]aneN(3) units play very important role in their catalytic synergistic effects.

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Ten-Membered Rings or Lager With One or More Nitrogen Atoms

Hermann

Kotek

Kubíček

2022

Comprehensive Heterocyclic Chemistry IV

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Efficient syntheses of artificial nucleases containing mono-, di- and tri-[12]aneN3 ligating units through click chemistry

Cited by 7 publications

References 26 publications

Steric effects on the catalytic activities of zinc(ii) complexes containing [12]aneN3 ligating units in the cleavage of the RNA and DNA model phosphates

Steric effects on the catalytic activities of zinc(ii) complexes containing [12]aneN3 ligating units in the cleavage of the RNA and DNA model phosphates

Synthesis of mono- and di-[12]aneN3 ligands and study on the catalytic cleavage of RNA model 2-hydroxypropyl-p-nitrophenyl phosphate with their metal complexes

Ten-Membered Rings or Lager With One or More Nitrogen Atoms

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