Selective Reactions on the
Azido Groups of Aromatic Polyazides

Чапышев, С. В.

doi:10.1055/s-0028-1087479

Cited by 14 publications

(14 citation statements)

References 42 publications

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“…Aromatic polyazides are widely used as starting materials in organic synthesis and as photoactive cross‐linking reagents in polymer chemistry and lithography . When aromatic polyazides have two or more nonequivalent azido groups, these groups can selectively react with dipolarophiles, electrophiles, nucleophiles and reductants or undergo selective thermolysis and photolysis . Recently, we have reported the synthesis and some chemical transformations of triazides 1–6 (Scheme ) .…”

Section: Introductionmentioning

confidence: 99%

¹⁵N NMR spectra and reactivity of 2,4,6‐triazidopyridines, 2,4,6‐triazidopyrimidine and 2,4,6‐triazido‐s‐triazine

Чапышев

Ushakov

Chernyak

2013

Magnetic Reson in Chemistry

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2,4,6-Triazido-s-triazine, 2,4,6-triazidopyrimidine and six different 2,4,6-triazidopyridines were studied by (15)N NMR spectroscopy. The assignment of signals in the spectra was performed using the gauge-independent atomic orbital (GIAO)-Tao-Perdew-Staroverov-Scuseria exchange-correlation functional (TPSS)h/6-311+G(d,p) calculations on the M06-2X/6-311+G(d,p) optimized molecular geometries. The Truhlar and coworkers' continuum solvation model called SMD was applied to treat solvent effects. With this approach, the root mean square error in estimations of the (15)N chemical shifts for the azido groups was just 1.9 ppm. It was shown that the different reactivity of the α- and γ-azido groups in pyridines correlates well with the chemical shifts of the Nα signals of these groups. Of two nonequivalent azido groups of azines, the azido group with the most shielded Nα signal is the most electron-deficient and reactive toward electron-rich reagents. By contrast, the azido group of azines with the most deshielded Nα signal is the most reactive toward electron-poor reagents.

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Section: Introductionmentioning

confidence: 99%

¹⁵N NMR spectra and reactivity of 2,4,6‐triazidopyridines, 2,4,6‐triazidopyrimidine and 2,4,6‐triazido‐s‐triazine

Чапышев

Ushakov

Chernyak

2013

Magnetic Reson in Chemistry

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“…past decades, 8,59,79,80,82,94,98,99 whereas the chelating behavior of donor-functionalized 3H-1,2,3,4-triaza-phosphole derivatives is still practically uncharted. [100][101][102] Clearly speaking, the click reaction between donor-functionalized azides and phosphaalkynes enables access to polydentate ligands, so that we can adjust the stereoelectronic properties based on the additional phosphorus heteroatom and the nature of the substituents. However, few investigations have been performed on the inuence of an additional heteroatom on the properties of triazole derivatives.…”

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confidence: 99%

Computational investigations of click-derived 1,2,3-triazoles as keystone ligands for complexation with transition metals: a review

2018

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In recent years, metal complexes of organo 1,2,3-triazole click-derived ligands have attracted significant attention as catalysts in many chemical transformations and also as biological and pharmaceutical active agents. Regarding the important applications of these metal-organo 1,2,3-triazole-based complexes, in this review, we focused on the recently reported investigations of the structural, electronic, and spectroscopic aspects of the complexation process in transition metal complexes of 1,2,3-triazole-based click ligands. In line with this, the coordination properties of these triazole-based click ligands with transition metals were studied via several quantum chemistry calculations. Moreover, considering the complexation process, we have presented comparative discussions between the computational results and the available experimental data.

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“…One of the most interesting features of 2,4,6‐triazidopyridines is a chemical non‐equivalence of the α‐azido and γ‐azido groups. Extensive studies have shown that reactions of triazide 1 with electron‐rich reagents occur selectively on the most electron‐deficient γ‐azido group, while reactions of electron‐poor reagents with 1 take place selectively on the α‐azido groups (Scheme ) . The different reactivity of the α‐azido and γ‐azido groups of 2,4,6‐triazidopyridines correlates well with the 15 N chemical shifts of the N α signals of these groups .…”

Section: Resultsmentioning

confidence: 98%

¹³C and ¹⁵N NMR spectra of high‐energy polyazidocyanopyridines

Чапышев

Chernyak

Ushakov

2016

Magnetic Reson in Chemistry

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C and N NMR spectra of high-energy 2,4,6-triazidopyridine-3,5-dicarbonitrile, 2,3,5,6-tetraazidopyridine-4-carbonitrile and 3,4,5,6-tetraazidopyridine-2-carbonitrile are reported. The assignment of signals in the spectra was performed on the basis of density functional theory calculations. The molecular geometries were optimized using the M06-2X functional with the 6-311+G(d,p) basis set. The magnetic shielding tensors were calculated by the gauge-independent atomic orbital method with the Tao-Perdew-Staroverov-Scuseria hybrid functional known as TPSSh. In all the calculations, a polarizable continuum model was used to simulate solvent effects. This approach provided accurate predictions of the C and N chemical shifts for all the three compounds despite complications arising due to non-coplanar arrangement of the azido groups in the molecules. It was found that the N chemical shifts of the N atoms in the azido groups of 2,4,6-triazidopyridines correlate with the C chemical shifts of the carbon atoms attached to these azido groups. Copyright © 2016 John Wiley& Sons, Ltd.

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Selective Reactions on the Azido Groups of Aromatic Polyazides

Cited by 14 publications

References 42 publications

¹⁵N NMR spectra and reactivity of 2,4,6‐triazidopyridines, 2,4,6‐triazidopyrimidine and 2,4,6‐triazido‐s‐triazine

¹⁵N NMR spectra and reactivity of 2,4,6‐triazidopyridines, 2,4,6‐triazidopyrimidine and 2,4,6‐triazido‐s‐triazine

Computational investigations of click-derived 1,2,3-triazoles as keystone ligands for complexation with transition metals: a review

¹³C and ¹⁵N NMR spectra of high‐energy polyazidocyanopyridines

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Selective Reactions on the Azido Groups of Aromatic Polyazides

Cited by 14 publications

References 42 publications

15N NMR spectra and reactivity of 2,4,6‐triazidopyridines, 2,4,6‐triazidopyrimidine and 2,4,6‐triazido‐s‐triazine

15N NMR spectra and reactivity of 2,4,6‐triazidopyridines, 2,4,6‐triazidopyrimidine and 2,4,6‐triazido‐s‐triazine

Computational investigations of click-derived 1,2,3-triazoles as keystone ligands for complexation with transition metals: a review

13C and 15N NMR spectra of high‐energy polyazidocyanopyridines

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¹⁵N NMR spectra and reactivity of 2,4,6‐triazidopyridines, 2,4,6‐triazidopyrimidine and 2,4,6‐triazido‐s‐triazine

¹⁵N NMR spectra and reactivity of 2,4,6‐triazidopyridines, 2,4,6‐triazidopyrimidine and 2,4,6‐triazido‐s‐triazine

¹³C and ¹⁵N NMR spectra of high‐energy polyazidocyanopyridines