Issue 19, 2011

Synthesis of mono- and di-[12]aneN3ligands and study on the catalytic cleavage of RNA model 2-hydroxypropyl-p-nitrophenyl phosphate with their metal complexes

Abstract

A series of mono- and di-[12]aneN3 ligands 1–6, which contain different substituents on the coordinating backbone, different linkers between two [12]aneN3 units and different N-methylation on the [12]aneN3 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]aneN3 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 k2, dinuclear complexes Zn2-3b, Zn2-3d, Zn2-4b, and Cu2-4b afforded activities of 7.9 × 105, 3.9 × 104, 9.0 × 104, and 8.1 × 104-fold higher than that of methoxide. The ortho arrangement of the two [12]aneN3 units and the presence of 5- or 2-positioned substituents in the benzene ring as well as N-methylation of [12]aneN3 units greatly reduced the catalytic activities due to the steric effects. These results clearly indicate that the structures of the linker between two [12]aneN3 units play very important role in their catalytic synergistic effects.

Graphical abstract: 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

Supplementary files

Article information

Article type
Paper
Submitted
11 Jun 2011
Accepted
22 Jul 2011
First published
25 Jul 2011

Org. Biomol. Chem., 2011,9, 6788-6796

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

Z. Guo, H. Yan, Z. Li and Z. Lu, Org. Biomol. Chem., 2011, 9, 6788 DOI: 10.1039/C1OB05942D

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