Mesomeric Betaines Based on Adamantylated 1,2,4-Triazolo[4,3-a]pyrimidin-5-ones: Synthesis, Structure and Conversion into Anionic N-Heterocyclic Carbenes

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Mesomeric Betaines Based on Adamantylated 1,2,4-Triazolo[4,3-a]pyrimidin-5-ones: Synthesis, Structure and Conversion into Anionic N-Heterocyclic Carbenes. / Sheina, Ekaterina S.; Shestakova, Tatyana S.; Deev, Sergey L. и др.
в: Chemistry - An Asian Journal, Том 18, № 5, e202201306, 01.03.2023.

Результаты исследований: Вклад в журнал › Статья › Рецензирование

BibTeX

@article{bfe2ee20c0c04ffe8047557a936e0961,

title = "Mesomeric Betaines Based on Adamantylated 1,2,4-Triazolo[4,3-a]pyrimidin-5-ones: Synthesis, Structure and Conversion into Anionic N-Heterocyclic Carbenes",

abstract = "The C−N coupling of 1,2,4-triazolo[1,5-a]pyrimidin-7-ones with 1-adamantanol/1-bromoadamantane leads to 1,2,4-triazolo[4,3-a]pyrimidinium-5-olates, which are represented as mesomeric betaines (MBs). The formation of MBs involves not only N-alkylation of heterocyclic framework but also the rearrangement leading to a change in the type of fusion between pyrimidine and 1,2,4-triazole fragments. The structures of the obtained products were confirmed by the X-ray analysis and measurements of 13C−13C (JCC) coupling constants in the 1D 13C NMR spectra of selectively 13C-labeled samples. Treatment of the betaines with lithium bis(trimethylsilyl)amide (LiHMDS) gave anionic carbenes, which were detected by 13C NMR spectroscopy and were trapped by reactions with phenyl isothiocyanate and sulfur. Density functional theory (DFT) and the quantum theory of atoms in molecules (QTAIM) analyses allowed for an insight into the electronic structure of the obtained betaines and N-heterocyclic carbene derivatives.",

author = "Sheina, {Ekaterina S.} and Shestakova, {Tatyana S.} and Deev, {Sergey L.} and Khalymbadzha, {Igor A.} and Slepukhin, {Pavel A.} and Eltsov, {Oleg S.} and Novikov, {Alexander S.} and Shevyrin, {Vadim A.} and Charushin, {Valery N.} and Chupakhin, {Oleg N.}",

note = "This work was supported by the Russian Foundation for Basic Research (Grant No. 20‐03‐00842) and the Ministry of Science and Higher Education of the Russian Federation (State Contract No. FEUZ‐2023‐0021 (H687.42B.325/23)). Alexander S. Novikov is grateful to RUDN University for support within the Strategic Academic Leadership Program.",

year = "2023",

month = mar,

day = "1",

doi = "10.1002/asia.202201306",

language = "English",

volume = "18",

journal = "Chemistry - An Asian Journal",

issn = "1861-4728",

publisher = "Wiley-VCH Verlag",

number = "5",

}

RIS

TY - JOUR

T1 - Mesomeric Betaines Based on Adamantylated 1,2,4-Triazolo[4,3-a]pyrimidin-5-ones: Synthesis, Structure and Conversion into Anionic N-Heterocyclic Carbenes

AU - Sheina, Ekaterina S.

AU - Shestakova, Tatyana S.

AU - Deev, Sergey L.

AU - Khalymbadzha, Igor A.

AU - Slepukhin, Pavel A.

AU - Eltsov, Oleg S.

AU - Novikov, Alexander S.

AU - Shevyrin, Vadim A.

AU - Charushin, Valery N.

AU - Chupakhin, Oleg N.

N1 - This work was supported by the Russian Foundation for Basic Research (Grant No. 20‐03‐00842) and the Ministry of Science and Higher Education of the Russian Federation (State Contract No. FEUZ‐2023‐0021 (H687.42B.325/23)). Alexander S. Novikov is grateful to RUDN University for support within the Strategic Academic Leadership Program.

PY - 2023/3/1

Y1 - 2023/3/1

N2 - The C−N coupling of 1,2,4-triazolo[1,5-a]pyrimidin-7-ones with 1-adamantanol/1-bromoadamantane leads to 1,2,4-triazolo[4,3-a]pyrimidinium-5-olates, which are represented as mesomeric betaines (MBs). The formation of MBs involves not only N-alkylation of heterocyclic framework but also the rearrangement leading to a change in the type of fusion between pyrimidine and 1,2,4-triazole fragments. The structures of the obtained products were confirmed by the X-ray analysis and measurements of 13C−13C (JCC) coupling constants in the 1D 13C NMR spectra of selectively 13C-labeled samples. Treatment of the betaines with lithium bis(trimethylsilyl)amide (LiHMDS) gave anionic carbenes, which were detected by 13C NMR spectroscopy and were trapped by reactions with phenyl isothiocyanate and sulfur. Density functional theory (DFT) and the quantum theory of atoms in molecules (QTAIM) analyses allowed for an insight into the electronic structure of the obtained betaines and N-heterocyclic carbene derivatives.

AB - The C−N coupling of 1,2,4-triazolo[1,5-a]pyrimidin-7-ones with 1-adamantanol/1-bromoadamantane leads to 1,2,4-triazolo[4,3-a]pyrimidinium-5-olates, which are represented as mesomeric betaines (MBs). The formation of MBs involves not only N-alkylation of heterocyclic framework but also the rearrangement leading to a change in the type of fusion between pyrimidine and 1,2,4-triazole fragments. The structures of the obtained products were confirmed by the X-ray analysis and measurements of 13C−13C (JCC) coupling constants in the 1D 13C NMR spectra of selectively 13C-labeled samples. Treatment of the betaines with lithium bis(trimethylsilyl)amide (LiHMDS) gave anionic carbenes, which were detected by 13C NMR spectroscopy and were trapped by reactions with phenyl isothiocyanate and sulfur. Density functional theory (DFT) and the quantum theory of atoms in molecules (QTAIM) analyses allowed for an insight into the electronic structure of the obtained betaines and N-heterocyclic carbene derivatives.

UR - http://www.scopus.com/inward/record.url?scp=85147007061&partnerID=8YFLogxK

U2 - 10.1002/asia.202201306

DO - 10.1002/asia.202201306

M3 - Article

VL - 18

JO - Chemistry - An Asian Journal

JF - Chemistry - An Asian Journal

SN - 1861-4728

IS - 5

M1 - e202201306

ER -

ID: 35853268