Generation and cascade reactions of N-[1,2-bis(methoxycarbonyl)vinyl]pyridinium species

Rzhevskiy, Sergey A.; Topchiy, Maxim A.; Bogachev, Vasilii N.; Minaeva, Lidiya I.; Cherkashchenko, Ilia R.; Lavrov, K. V.; Sterligov, Grigorii K.; Nechaev, Mikhail S.; Asachenko, Andrey F.

doi:10.1016/j.mencom.2022.03.037

Cited by 4 publications

(18 citation statements)

References 65 publications

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“…The experimental section has no title; please leave this line here. 1 H NMR and 13 C NMR spectra were recorded on a «Bruker AVANCE II 300» spectrometer at 300 and 75 MHz, respectively, in CDCl3 with tetramethylsilane as an internal reference standard, and DMSO-d6.…”

Section: Synthesismentioning

confidence: 99%

Cyсlopentadienone and Pyrone Derivatives as Precursors of Electron-Deficient Cycloheptatrienes: Quantum Chemical Investigation and Synthesis

Salikov,

Tomilov,

Sokolova

et al. 2024

Synthesis

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Unstable tetra(methoxycarbonyl)cyclopentadienone was investigated in the synthesis of electron-deficient cycloheptatrienes via [4+2]-cycloaddition/cycloelimination reaction with cyclopropenes. The use of its stable dimer did not afford the product although similar reactions with alkynes have been reported. Quantum chemical calculation revealed that cyclopentadienone is not generated from the dimer and the reaction with alkynes proceeds via a more complicated cycloelimination/cycloaddition/cycloelimination cascade. However, the formation of cycloheptatrienes was found favorable over the formation of the dimer. Therefore, the trapping of tetra(methoxycarbonyl)cyclopentadienone upon formation was successful to give cycloheptatrienes with five ester groups. The use of methyl coumalate as a four-electron component was successful with cyclopropenes containing only one ester group to afford only two ester groups in the product.

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Section: Synthesismentioning

confidence: 99%

Cyсlopentadienone and Pyrone Derivatives as Precursors of Electron-Deficient Cycloheptatrienes: Quantum Chemical Investigation and Synthesis

Salikov,

Tomilov,

Sokolova

et al. 2024

Synthesis

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“…In both cases, the intermediate cycloheptadienyl anion is formed via an electrocyclic ring-closure and is either protonated to yield a mixture of isomeric cycloheptadienes or eliminates a leaving group (pyridine) with the formation of cycloheptatriene. Closely related malononitrile in the very same reaction yields only a linear C 1 + 2C 2 acyclic product, presumably due to the higher anion-stabilizing nature of the two cyano groups that suppresses the third vinylation . Thus, the appropriate acidity of the utilized CH-acid can be regarded as one of the key conditions for the successful cascade reaction.…”

Section: Introductionmentioning

confidence: 99%

“…16,24−28 Previously, 1,2-(dimethoxycarbonyl)vinylpyridinium (VP) was established as an easily generated and highly electrophilic vinylative reagent (Scheme 1B). 29 A number of CH-acids have been tested in the given reaction; however, only dimethylmalonate 25 and methoxycarbonylmethylpyridinium 24 gave seven-membered products. In both cases, the intermediate cycloheptadienyl anion is formed via an electrocyclic ring-closure and is either protonated to yield a mixture of isomeric cycloheptadienes or eliminates a leaving group (pyridine) with the formation of cycloheptatriene.…”

Section: ■ Introductionmentioning

confidence: 99%

“…Closely related malononitrile in the very same reaction yields only a linear C 1 + 2C 2 acyclic product, presumably due to the higher anion-stabilizing nature of the two cyano groups that suppresses the third vinylation. 29 Thus, the appropriate acidity of the utilized CH-acid can be regarded as one of the key conditions for the successful cascade reaction.…”

Section: ■ Introductionmentioning

confidence: 99%

“…This disconnection is convenient for the synthesis of electron-deficient seven-membered systems since the nature of both nucleophilic and electrophilic reagents imply the presence of electron-withdrawing groups. The synthetic path based on such a disconnection includes three vinylation steps of the CH-acid followed by 8π-electrocyclizationa powerful transformation to assemble a seven-membered ring from an acyclic substrate; yet it is highly restricted by the availability of conjugated heptatrienyl anions and therefore rarely utilized. ,− Previously, 1,2-(dimethoxycarbonyl)vinylpyridinium (VP) was established as an easily generated and highly electrophilic vinylative reagent (Scheme B) . A number of CH-acids have been tested in the given reaction; however, only dimethylmalonate and methoxycarbonylmethylpyridinium gave seven-membered products.…”

Section: Introductionmentioning

confidence: 99%

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Cascade Vinylation/8π-Electrocyclization and Cu(II)-Catalyzed Dehydrogenation toward Highly Stable Formally Antiaromatic Cycloheptatrienyl Anions

et al. 2023

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An approach to the synthesis of seven-membered systems via the chain elongation of nucleophilic propenes and subsequent 8π-electrocyclization is proposed. The cascade reaction yields either cycloheptadienes or bicycloheptenes, and the latter are formed via a 6π-electrocyclization of intermediate cycloheptadienyl anion which was proved to be reversible in a basic medium. The electrocyclic nature of the ring-closing reactions was supported by density functional theory and DLPNO/CCSD(T) calculations. Highly electron-deficient cycloheptatrienes can be obtained from cycloheptadienes or bicycloheptenes via oxidation either introduced into the cascade reaction or performed as a separate reaction, with the overall yield of up to 81%. The oxidation step was performed by means of a rarely encountered Cu(II)-catalyzed dehydrogenation of cycloheptadienes or bicycloheptenes, and so the reaction mechanism was proposed. Stable formally 8π-antiaromatic cycloheptatrienyl-anion containing compounds were obtained, and some correlations between their UV−vis spectra and the structure of the distorted cycloheptatrienyl-anion moiety were clarified. Additionally, a base-induced retro-[2 + 2]-cycloaddition in a bicycloheptene derivative gave cyanotetra-(methoxycarbonyl)cyclopentadienyl cesium.

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Investigation of reactions of CH-acids with generated in situ N-[1,2-bis(methoxycarbonyl)vinyl]pyridinium in the synthesis of 1,2,3,4,5,6,7-hepta(methoxycarbonyl)cycloheptatriene

Belyy,

Sokolova,

Salikov

et al. 2024

Russ Chem Bull

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Generation and cascade reactions of N-[1,2-bis(methoxycarbonyl)vinyl]pyridinium species

Cited by 4 publications

References 65 publications

Cyсlopentadienone and Pyrone Derivatives as Precursors of Electron-Deficient Cycloheptatrienes: Quantum Chemical Investigation and Synthesis

Cyсlopentadienone and Pyrone Derivatives as Precursors of Electron-Deficient Cycloheptatrienes: Quantum Chemical Investigation and Synthesis

Cascade Vinylation/8π-Electrocyclization and Cu(II)-Catalyzed Dehydrogenation toward Highly Stable Formally Antiaromatic Cycloheptatrienyl Anions

Investigation of reactions of CH-acids with generated in situ N-[1,2-bis(methoxycarbonyl)vinyl]pyridinium in the synthesis of 1,2,3,4,5,6,7-hepta(methoxycarbonyl)cycloheptatriene

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