Theoretical investigation of tautomerism of 2- and 4-pyridones: origin, substituent and solvent effects
Само за регистроване кориснике
2023
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Computational investigation at the BHandHLYP/6-311+G(d,p) level of theory of the gas-phase tautomerism of 2- and 4-pyridones confirmed the slight prevalence of lactim in the case of the former, but its dominance in the case of the latter, as shown previously. Examination of aromaticity by using HOMA, EDDB, NBOdel, NICS and AICD led to the conclusion that tautomerization of 4-pyridone results in greater aromaticity gain. It is also driven by the Pauli repulsion relief, which was revealed by the tautomerization energy decomposition analysis. By contrast, in the case of 2-pyridone, lactim is favoured by orbital and electrostatic interactions and disfavoured by the Pauli repulsion. Aromaticity gain in this case is smaller. The position of the tautomeric equilibrium can be modulated by substituent inductive effects (Cl and F), inductive and resonance effects (NH2 and NO2), hydrogen bonding (NO2), and medium polarity, the increase of which increases lactam population.
Кључне речи:
tautomerism / computational chemistryИзвор:
Organic & Biomolecular Chemistry, 2023, 22, 1, 144-158Издавач:
- Royal Society of Chemistry (RSC)
Финансирање / пројекти:
- Министарство науке, технолошког развоја и иновација Републике Србије, институционално финансирање - 200168 (Универзитет у Београду, Хемијски факултет) (RS-MESTD-inst-2020-200168)
- Министарство науке, технолошког развоја и иновација Републике Србије, институционално финансирање - 200026 (Универзитет у Београду, Институт за хемију, технологију и металургију - ИХТМ) (RS-MESTD-inst-2020-200026)
Институција/група
IHTMTY - JOUR AU - Baranac-Stojanović, Marija AU - Aleksić, Jovana AU - Stojanović, Milovan PY - 2023 UR - https://cer.ihtm.bg.ac.rs/handle/123456789/7229 AB - Computational investigation at the BHandHLYP/6-311+G(d,p) level of theory of the gas-phase tautomerism of 2- and 4-pyridones confirmed the slight prevalence of lactim in the case of the former, but its dominance in the case of the latter, as shown previously. Examination of aromaticity by using HOMA, EDDB, NBOdel, NICS and AICD led to the conclusion that tautomerization of 4-pyridone results in greater aromaticity gain. It is also driven by the Pauli repulsion relief, which was revealed by the tautomerization energy decomposition analysis. By contrast, in the case of 2-pyridone, lactim is favoured by orbital and electrostatic interactions and disfavoured by the Pauli repulsion. Aromaticity gain in this case is smaller. The position of the tautomeric equilibrium can be modulated by substituent inductive effects (Cl and F), inductive and resonance effects (NH2 and NO2), hydrogen bonding (NO2), and medium polarity, the increase of which increases lactam population. PB - Royal Society of Chemistry (RSC) T2 - Organic & Biomolecular Chemistry T1 - Theoretical investigation of tautomerism of 2- and 4-pyridones: origin, substituent and solvent effects VL - 22 IS - 1 SP - 144 EP - 158 DO - 10.1039/D3OB01588B ER -
@article{ author = "Baranac-Stojanović, Marija and Aleksić, Jovana and Stojanović, Milovan", year = "2023", abstract = "Computational investigation at the BHandHLYP/6-311+G(d,p) level of theory of the gas-phase tautomerism of 2- and 4-pyridones confirmed the slight prevalence of lactim in the case of the former, but its dominance in the case of the latter, as shown previously. Examination of aromaticity by using HOMA, EDDB, NBOdel, NICS and AICD led to the conclusion that tautomerization of 4-pyridone results in greater aromaticity gain. It is also driven by the Pauli repulsion relief, which was revealed by the tautomerization energy decomposition analysis. By contrast, in the case of 2-pyridone, lactim is favoured by orbital and electrostatic interactions and disfavoured by the Pauli repulsion. Aromaticity gain in this case is smaller. The position of the tautomeric equilibrium can be modulated by substituent inductive effects (Cl and F), inductive and resonance effects (NH2 and NO2), hydrogen bonding (NO2), and medium polarity, the increase of which increases lactam population.", publisher = "Royal Society of Chemistry (RSC)", journal = "Organic & Biomolecular Chemistry", title = "Theoretical investigation of tautomerism of 2- and 4-pyridones: origin, substituent and solvent effects", volume = "22", number = "1", pages = "144-158", doi = "10.1039/D3OB01588B" }
Baranac-Stojanović, M., Aleksić, J.,& Stojanović, M.. (2023). Theoretical investigation of tautomerism of 2- and 4-pyridones: origin, substituent and solvent effects. in Organic & Biomolecular Chemistry Royal Society of Chemistry (RSC)., 22(1), 144-158. https://doi.org/10.1039/D3OB01588B
Baranac-Stojanović M, Aleksić J, Stojanović M. Theoretical investigation of tautomerism of 2- and 4-pyridones: origin, substituent and solvent effects. in Organic & Biomolecular Chemistry. 2023;22(1):144-158. doi:10.1039/D3OB01588B .
Baranac-Stojanović, Marija, Aleksić, Jovana, Stojanović, Milovan, "Theoretical investigation of tautomerism of 2- and 4-pyridones: origin, substituent and solvent effects" in Organic & Biomolecular Chemistry, 22, no. 1 (2023):144-158, https://doi.org/10.1039/D3OB01588B . .