Brønsted acid promoted reactions of -hydroxy acetylene ketones. DFT study of cationic intermediates, and concurrent formation of 3-furanones and/or conjugated enynones

Standard

Brønsted acid promoted reactions of -hydroxy acetylene ketones. DFT study of cationic intermediates, and concurrent formation of 3-furanones and/or conjugated enynones. / Боярская, Ирина Алексеевна; Хорошилова, Олеся Валерьевна; Каляев, Михаил Владимирович ; Васильев, Александр Викторович.

In: Russian Journal of General Chemistry, Vol. 94, No. Suppl 1, 01.01.2024, p. S138-S147.

Research output: Contribution to journal › Article › peer-review

BibTeX

@article{467a2f6777164dce9cfd84e6f5b9af62,

title = "Br{\o}nsted acid promoted reactions of -hydroxy acetylene ketones. DFT study of cationic intermediates, and concurrent formation of 3-furanones and/or conjugated enynones",

abstract = "Abstract: Protonation of γ-hydroxy conjugated acetylene ketones Ph(O=)C–C≡C–C(OH)R1R2 in strong Br{\o}nsted acid H2SO4 or superacid TfOH (CF3SO3H, triflic acid) gives rise to O,O-diprotonated species Ph(+HO=)C–C≡C–C(OH2+)R1R2. Electrophilic, electronic and orbital properties of these dications have been studied by DFT calculations. Depending on the structure of the dications and acidity of Br{\o}nsted acid (nucleophilicity of the corresponding acid counter ion), two concurrent reaction products may be formed, 3(2H)-furanones in a way of cyclization and/or conjugated enynones in a way of dehydration. Plausible reaction mechanisms are discussed.",

keywords = "монофторирование, окисление, фтористый водород, 3-furanones, acetylene ketones, carbocations, enynones, propargyl alcohols",

author = "Боярская, {Ирина Алексеевна} and Хорошилова, {Олеся Валерьевна} and Каляев, {Михаил Владимирович} and Васильев, {Александр Викторович}",

note = "Kuzmin A.A., Boyarskaya I.A., Khoroshilova O.V., Kalyaev M.V., Vasilyev A.V. Br{\o}nsted acid promoted reactions of -hydroxy acetylene ketones. DFT study of cationic intermediates, and concurrent formation of 3-furanones and/or conjugated enynones. Russian Journal of General Chemistry. 2024, V. 94, Suppl. 1, P. S138-S147.",

year = "2024",

month = jan,

day = "1",

doi = "10.1134/s1070363224140147",

language = "English",

volume = "94",

pages = "S138--S147",

journal = "Russian Journal of General Chemistry",

issn = "1070-3632",

publisher = "МАИК {"}Наука/Интерпериодика{"}",

number = "Suppl 1",

}

RIS

TY - JOUR

T1 - Brønsted acid promoted reactions of -hydroxy acetylene ketones. DFT study of cationic intermediates, and concurrent formation of 3-furanones and/or conjugated enynones

AU - Боярская, Ирина Алексеевна

AU - Хорошилова, Олеся Валерьевна

AU - Каляев, Михаил Владимирович

AU - Васильев, Александр Викторович

N1 - Kuzmin A.A., Boyarskaya I.A., Khoroshilova O.V., Kalyaev M.V., Vasilyev A.V. Brønsted acid promoted reactions of -hydroxy acetylene ketones. DFT study of cationic intermediates, and concurrent formation of 3-furanones and/or conjugated enynones. Russian Journal of General Chemistry. 2024, V. 94, Suppl. 1, P. S138-S147.

PY - 2024/1/1

Y1 - 2024/1/1

N2 - Abstract: Protonation of γ-hydroxy conjugated acetylene ketones Ph(O=)C–C≡C–C(OH)R1R2 in strong Brønsted acid H2SO4 or superacid TfOH (CF3SO3H, triflic acid) gives rise to O,O-diprotonated species Ph(+HO=)C–C≡C–C(OH2+)R1R2. Electrophilic, electronic and orbital properties of these dications have been studied by DFT calculations. Depending on the structure of the dications and acidity of Brønsted acid (nucleophilicity of the corresponding acid counter ion), two concurrent reaction products may be formed, 3(2H)-furanones in a way of cyclization and/or conjugated enynones in a way of dehydration. Plausible reaction mechanisms are discussed.

AB - Abstract: Protonation of γ-hydroxy conjugated acetylene ketones Ph(O=)C–C≡C–C(OH)R1R2 in strong Brønsted acid H2SO4 or superacid TfOH (CF3SO3H, triflic acid) gives rise to O,O-diprotonated species Ph(+HO=)C–C≡C–C(OH2+)R1R2. Electrophilic, electronic and orbital properties of these dications have been studied by DFT calculations. Depending on the structure of the dications and acidity of Brønsted acid (nucleophilicity of the corresponding acid counter ion), two concurrent reaction products may be formed, 3(2H)-furanones in a way of cyclization and/or conjugated enynones in a way of dehydration. Plausible reaction mechanisms are discussed.

KW - монофторирование, окисление, фтористый водород

KW - 3-furanones

KW - acetylene ketones

KW - carbocations

KW - enynones

KW - propargyl alcohols

UR - https://link.springer.com/article/10.1134/S1070363224140147

UR - https://www.mendeley.com/catalogue/5ed3b00e-d585-3fec-9322-55065b1ca405/

U2 - 10.1134/s1070363224140147

DO - 10.1134/s1070363224140147

M3 - Article

VL - 94

SP - S138-S147

JO - Russian Journal of General Chemistry

JF - Russian Journal of General Chemistry

SN - 1070-3632

IS - Suppl 1

ER -

ID: 126750714