Synthesis 2024; 56(16): 2581-2587
DOI: 10.1055/a-2317-6659
paper

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

Alena D. Sokolova
a   N. D. Zelinsky Institute of Organic Chemistry, Russian Academy of Sciences, 47 Leninsky prosp., 119991 Moscow, Russian Federation
,
Alexander Yu. Belyy
a   N. D. Zelinsky Institute of Organic Chemistry, Russian Academy of Sciences, 47 Leninsky prosp., 119991 Moscow, Russian Federation
,
a   N. D. Zelinsky Institute of Organic Chemistry, Russian Academy of Sciences, 47 Leninsky prosp., 119991 Moscow, Russian Federation
b   Higher School of Economics National Research University, 101000 Moscow, Russian Federation
,
Dmitry N. Platonov
a   N. D. Zelinsky Institute of Organic Chemistry, Russian Academy of Sciences, 47 Leninsky prosp., 119991 Moscow, Russian Federation
,
Yury V. Tomilov
a   N. D. Zelinsky Institute of Organic Chemistry, Russian Academy of Sciences, 47 Leninsky prosp., 119991 Moscow, Russian Federation
› Institutsangaben
The work was supported by the Russian Science Foundation (Grant No. 23-73-10181).


Abstract

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.

Supporting Information



Publikationsverlauf

Eingereicht: 05. April 2024

Angenommen nach Revision: 30. April 2024

Accepted Manuscript online:
30. April 2024

Artikel online veröffentlicht:
13. Mai 2024

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