Reactions of dimethyl ester of acetylene dicarboxylic acid (DMAD) with arenes under the superelectrophilic activation conditions.

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Reactions of dimethyl ester of acetylene dicarboxylic acid (DMAD) with arenes under the superelectrophilic activation conditions. / Коноплев, Михаил Витальевич; Хорошилова, Олеся Валерьевна; Боярская, Ирина Алексеевна; Спиридонова, Дарья Валерьевна; Васильев, Александр Викторович.

в: ChemistrySelect, Том 10, № 5, e202500383, 20.02.2025.

Результаты исследований: Научные публикации в периодических изданиях › статья › Рецензирование

BibTeX

@article{e17f6a188b6545a2a84c0c717bf0d67d,

title = "Reactions of dimethyl ester of acetylene dicarboxylic acid (DMAD) with arenes under the superelectrophilic activation conditions.",

abstract = "Protonation of DMAD MeO2C−C≡C−CO2Me in the Br{\o}nsted superacid CF3SO3H (triflic acid, TfOH) gives rise to stable O,O-diprotonated species MeO(+HO═)C−C≡C−C(═OH+)OMe according to NMR data and DFT calculation. This cation reacts with arenes ArH at room temperature for 0.3-1 h with a stereoselective formation of the corresponding trans-dimethyl arylfumarates E-MeO2C−C(Ar)═CH−CO2Me, as products of hydroarylation of the DMAD acetylene bond. Increasing the reaction time leads to further, deeper inter- and intramolecular transformations of dimethyl arylfumarates with arenes, resulting in various compounds, indenes, indenones, and indanones, that depend on the nucleiphilicity of arenes and reaction time. Plausible mechanisms of multistep cationic transformations of DMAD with arenes in TfOH are discussed.",

keywords = "Arylfumarates, Dimethyl ester of acetylene dicarboxylic acid (DMAD), Indane derivatives, Superelectrophilic activation, Triflic acid",

author = "Коноплев, {Михаил Витальевич} and Хорошилова, {Олеся Валерьевна} and Боярская, {Ирина Алексеевна} and Спиридонова, {Дарья Валерьевна} and Васильев, {Александр Викторович}",

note = "Konoplev M.V., Khoroshilova O.V., Boyarskaya I.A., Spiridonova D.V., Vasilyev A.V. Reactions of dimethyl ester of acetylene dicarboxylic acid (DMAD) with arenes under the superelectrophilic activation conditions. ChemistrySelect. 2025, V. 10, Iss. 5, e202500383.",

year = "2025",

month = feb,

day = "20",

doi = "10.1002/slct.202500383",

language = "English",

volume = "10",

journal = "ChemistrySelect",

issn = "2365-6549",

publisher = "Wiley-Blackwell",

number = "5",

}

RIS

TY - JOUR

T1 - Reactions of dimethyl ester of acetylene dicarboxylic acid (DMAD) with arenes under the superelectrophilic activation conditions.

AU - Коноплев, Михаил Витальевич

AU - Хорошилова, Олеся Валерьевна

AU - Боярская, Ирина Алексеевна

AU - Спиридонова, Дарья Валерьевна

AU - Васильев, Александр Викторович

N1 - Konoplev M.V., Khoroshilova O.V., Boyarskaya I.A., Spiridonova D.V., Vasilyev A.V. Reactions of dimethyl ester of acetylene dicarboxylic acid (DMAD) with arenes under the superelectrophilic activation conditions. ChemistrySelect. 2025, V. 10, Iss. 5, e202500383.

PY - 2025/2/20

Y1 - 2025/2/20

N2 - Protonation of DMAD MeO2C−C≡C−CO2Me in the Brønsted superacid CF3SO3H (triflic acid, TfOH) gives rise to stable O,O-diprotonated species MeO(+HO═)C−C≡C−C(═OH+)OMe according to NMR data and DFT calculation. This cation reacts with arenes ArH at room temperature for 0.3-1 h with a stereoselective formation of the corresponding trans-dimethyl arylfumarates E-MeO2C−C(Ar)═CH−CO2Me, as products of hydroarylation of the DMAD acetylene bond. Increasing the reaction time leads to further, deeper inter- and intramolecular transformations of dimethyl arylfumarates with arenes, resulting in various compounds, indenes, indenones, and indanones, that depend on the nucleiphilicity of arenes and reaction time. Plausible mechanisms of multistep cationic transformations of DMAD with arenes in TfOH are discussed.

AB - Protonation of DMAD MeO2C−C≡C−CO2Me in the Brønsted superacid CF3SO3H (triflic acid, TfOH) gives rise to stable O,O-diprotonated species MeO(+HO═)C−C≡C−C(═OH+)OMe according to NMR data and DFT calculation. This cation reacts with arenes ArH at room temperature for 0.3-1 h with a stereoselective formation of the corresponding trans-dimethyl arylfumarates E-MeO2C−C(Ar)═CH−CO2Me, as products of hydroarylation of the DMAD acetylene bond. Increasing the reaction time leads to further, deeper inter- and intramolecular transformations of dimethyl arylfumarates with arenes, resulting in various compounds, indenes, indenones, and indanones, that depend on the nucleiphilicity of arenes and reaction time. Plausible mechanisms of multistep cationic transformations of DMAD with arenes in TfOH are discussed.

KW - Arylfumarates

KW - Dimethyl ester of acetylene dicarboxylic acid (DMAD)

KW - Indane derivatives

KW - Superelectrophilic activation

KW - Triflic acid

UR - https://www.mendeley.com/catalogue/77a235a2-0c49-3dd3-a2cc-77450a4dc3be/

U2 - 10.1002/slct.202500383

DO - 10.1002/slct.202500383

M3 - Article

VL - 10

JO - ChemistrySelect

JF - ChemistrySelect

SN - 2365-6549

IS - 5

M1 - e202500383

ER -

ID: 142467032