Synthesis of 4-Aryl-2-aminopyridine Derivatives and Related Compounds

Pavlović, Vera P.; Petković, Miloš; Popovic, Stanimir; Savić, Vladimir

doi:10.1080/00397910902898601

Cited by 11 publications

(5 citation statements)

References 5 publications

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“…grade were used as is with no further purification unless otherwise stated. [DMSOH] trans -[RuCl 4 (DMSO) 2 ] and [DMSOH] trans -[RhCl 4 (DMSO) 2 ] were prepared according to previously reported procedures. , Similarly, (4-cyanophenyl)pyridine and p -tolylpyridine were prepared according to reported procedures …”

Section: Methodsmentioning

confidence: 99%

“…36,37 Similarly, (4-cyanophenyl)pyridine and p-tolylpyridine were prepared according to reported procedures. 38 General Synthetic Procedure for Compounds 1−3, 5−8, 1b−3b, and 6b. Ru(III) and Rh(III) octahedral complexes with pyridine derivatives were synthesized in a manner similar to that reported by Webb and co-workers, 39 but in a slightly modified way.…”

Section: Introductionmentioning

confidence: 99%

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Interpreting the Paramagnetic NMR Spectra of Potential Ru(III) Metallodrugs: Synergy between Experiment and Relativistic DFT Calculations

et al. 2016

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Ruthenium-based compounds are potential candidates for use as anticancer metallodrugs. The central ruthenium atom can be in the oxidation state +2 (e.g., RAPTA, RAED) or +3 (e.g., NAMI, KP). In this study we focus on paramagnetic NAMI analogs of a general structure [4-R-pyH](+)trans-[Ru(III)Cl4(DMSO)(4-R-py)](-), where 4-R-py stands for a 4-substituted pyridine. As paramagnetic systems are generally considered difficult to characterize in detail by NMR spectroscopy, we performed a systematic structural and methodological NMR study of complexes containing variously substituted pyridines. The effect of the paramagnetic nature of these complexes on the (1)H and (13)C NMR chemical shifts was systematically investigated by temperature-dependent NMR experiments and density-functional theory (DFT) calculations. To understand the electronic factors influencing the orbital (δ(orb), temperature-independent) and paramagnetic (δ(para), temperature-dependent) contributions to the total NMR chemical shifts, a relativistic two-component DFT approach was used. The paramagnetic contributions to the (13)C NMR chemical shifts are correlated with the distribution of spin density in the ligand moiety and the (13)C isotropic hyperfine coupling constants, Aiso((13)C), for the individual carbon atoms. To analyze the mechanism of spin distribution in the ligand, the contributions of molecular spin-orbitals (MSOs) to the hyperfine coupling constants and the spatial distribution of the z-component of the spin density in the MSOs calculated at the relativistic four-component DFT level are discussed and rationalized. The significant effects of the substituent and the solvent on δ(para), particularly the contact contribution, are demonstrated. This work should contribute to further understanding of the link between the electronic structure and the NMR chemical shifts in open-shell systems, including the ruthenium-based metallodrugs investigated in this account.

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Section: Methodsmentioning

confidence: 99%

Section: Introductionmentioning

confidence: 99%

Interpreting the Paramagnetic NMR Spectra of Potential Ru(III) Metallodrugs: Synergy between Experiment and Relativistic DFT Calculations

et al. 2016

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“…4-(3-(Trifluoromethyl)phenyl)pyridine4-Aryl (3g). The compound 4-aryl (3g) (known compound) 88 was obtained following the general procedure. It was obtained in 18% yield (0.093 mmol, 20.7 mg) as a yellow oil after purification over silica gel column chromatography (hexane/EtOAc = from 9/1 (v/v) to 7/3 (v/v)).…”

Section: -(4-fluorophenyl)pyridine2-aryl (3d)mentioning

confidence: 99%

Photoarylation of Pyridines Using Aryldiazonium Salts and Visible Light: An EDA Approach

et al. 2019

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A metal-free methodology for the photoarylation of pyridines, in water, is described giving 2 and 4-arylated-pyridines in yields up to 96%. The scope of the aryldiazonium salts is presented showing important results depending on the nature and position of the substituent group in the diazonium salt, that is, electron-donating or electron-withdrawing in the ortho, meta, or para positions. Further heteroaromatics were also successfully photoarylated. Mechanistic studies and comparison between our methodology and similar metal-catalyzed procedures are presented, suggesting the occurrence of a visible-light EDA complex which generates the aryl radical with no need for an additional photocatalyst.

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“…Mp 58 °C; 1 H NMR (300 MHz, CDCl 3 ) δ 7.43 (dd, J = 3.0, 6.0 Hz, 1H), 7.46−7.55 (m, 4H), 7.60−7.63 (m, 2H), 8.43 (dd, J = 3.0, 6.0 Hz, 1H); 13 2-Chloro-4-(4-methylphenyl)pyridine (13). 68 The title compound 13 was obtained as a white solid (112 mg, 55% yield) after purification by silica gel column chromatography. Mp 50 °C; 1 H NMR (300 MHz, CDCl 3 ) δ 2.41 (s, 3H), 7.29 (d, J = 6.0 Hz, 2H), 7.40 (dd, J = 6.0, 3.0 Hz, 1H), 7.49−7.53 (m, 3H), 8.39 (d, J = 6.0 Hz, 1H); 13 2-Phenylpyridine (14).…”

Section: ■ Conclusionmentioning

confidence: 99%

General Copper-Catalyzed Coupling of Alkyl-, Aryl-, and Alkynylaluminum Reagents with Organohalides

et al. 2016

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We report the first example of a very general Cu-catalyzed cross-coupling of organoaluminum reagents with organohalides. The reactions proceed for the couplings of alkyl-, aryl-, and alkynylaluminum reagents with aryl and heteroaryl halides and vinyl bromides, affording the cross-coupled products in good to excellent yields. Both primary and secondary alkylaluminum reagents can be utilized as organometallic coupling partners. These reactions are not complicated by β-hydride elimination, and as a result rearranged products are not observed with secondary alkylaluminum reagents even for couplings with heteroaryl halides under "ligand-free" conditions. Radical clock experiment with a radical probe and relative reactivity study of Ph3Al with two haloarenes, 1-bromonaphthalene and 4-chlorobenzonitrile, having two different redox potentials indicates that the reaction does not involve free aryl radicals and radical anions as intermediates. These results combined with the result of the Hammett plot obtained by reacting Ph3Al with iodoarenes containing p-H, p-Me, p-F, and p-CF3 substituents, which shows a linear curve (R(2) = 0.99) with a ρ value of +1.06, suggest that the current transformation follows an oxidative addition-reductive elimination pathway.

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Synthesis of 4-Aryl-2-aminopyridine Derivatives and Related Compounds

Cited by 11 publications

References 5 publications

Interpreting the Paramagnetic NMR Spectra of Potential Ru(III) Metallodrugs: Synergy between Experiment and Relativistic DFT Calculations

Interpreting the Paramagnetic NMR Spectra of Potential Ru(III) Metallodrugs: Synergy between Experiment and Relativistic DFT Calculations

Photoarylation of Pyridines Using Aryldiazonium Salts and Visible Light: An EDA Approach

General Copper-Catalyzed Coupling of Alkyl-, Aryl-, and Alkynylaluminum Reagents with Organohalides

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