Generation and NMR Study of Short-Lived and Reactive Trifluoroalkyl Carbocations of the α-Halogenothiophene Series in Brønsted Superacids

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Generation and NMR Study of Short-Lived and Reactive Trifluoroalkyl Carbocations of the α-Halogenothiophene Series in Brønsted Superacids : Reactions of the Cations with Arenes. / Khoroshilova, Olesya V.; Vasilyev, Aleksander V.

в: Journal of Organic Chemistry, Том 85, № 9, 01.05.2020, стр. 5872-5883.

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

BibTeX

@article{c872542439a149c78a3d02a38c1a551c,

title = "Generation and NMR Study of Short-Lived and Reactive Trifluoroalkyl Carbocations of the α-Halogenothiophene Series in Br{\o}nsted Superacids: Reactions of the Cations with Arenes",

abstract = "Protonation of oxygen in the side chain of the Me3SiO group (followed by the elimination of Me3SiOH) and protonation of the thiophene ring in 2-chloro(or bromo)-5-(1′-Me3SiO-1′-trifluoromethyl-alkyl)thiophenes in Br{\o}nsted superacids (CF3SO3H, FSO3H) gave rise to short-lived and reactive trifluoroalkyl carbocations of the thiophene series. These cations were studied by low-temperature NMR spectroscopy in the superacids, which shed light on their reactivity and reaction mechanisms. The cations may react with (hetero)aromatic π-nucleophiles in various directions, depending on their structures as well as the reaction temperature and time. These transformations resulted in the formation of novel fluoro-organics of the thiophene family, namely, products of arylation of both the thiophene system and its side chain, hydrodehalogenation of halothiophenes, or electrophilic {"}dimerization{"}.",

keywords = "POLYMER SOLAR-CELLS, PROTONATED HALOTHIOPHENES, ELECTROPHILIC ACTIVATION, TMS-ETHERS, H-1-NMR, ACID",

author = "Khoroshilova, {Olesya V.} and Vasilyev, {Aleksander V.}",

note = "Funding Information: This work was supported by the Russian Scientific Foundation (grant no. 18-13-00008). Spectral studies were performed at the Center for Magnetic Resonance, the Center for Chemical Analysis and Materials Research, and the Research Center for X-ray Diffraction Studies of Saint Petersburg State University, Saint Petersburg, Russia. Publisher Copyright: Copyright {\textcopyright} 2020 American Chemical Society. Copyright: Copyright 2020 Elsevier B.V., All rights reserved.",

year = "2020",

month = may,

day = "1",

doi = "10.1021/acs.joc.0c00170",

language = "English",

volume = "85",

pages = "5872--5883",

journal = "Journal of Organic Chemistry",

issn = "0022-3263",

publisher = "American Chemical Society",

number = "9",

}

RIS

TY - JOUR

T1 - Generation and NMR Study of Short-Lived and Reactive Trifluoroalkyl Carbocations of the α-Halogenothiophene Series in Brønsted Superacids

T2 - Reactions of the Cations with Arenes

AU - Khoroshilova, Olesya V.

AU - Vasilyev, Aleksander V.

N1 - Funding Information: This work was supported by the Russian Scientific Foundation (grant no. 18-13-00008). Spectral studies were performed at the Center for Magnetic Resonance, the Center for Chemical Analysis and Materials Research, and the Research Center for X-ray Diffraction Studies of Saint Petersburg State University, Saint Petersburg, Russia. Publisher Copyright: Copyright © 2020 American Chemical Society. Copyright: Copyright 2020 Elsevier B.V., All rights reserved.

PY - 2020/5/1

Y1 - 2020/5/1

N2 - Protonation of oxygen in the side chain of the Me3SiO group (followed by the elimination of Me3SiOH) and protonation of the thiophene ring in 2-chloro(or bromo)-5-(1′-Me3SiO-1′-trifluoromethyl-alkyl)thiophenes in Brønsted superacids (CF3SO3H, FSO3H) gave rise to short-lived and reactive trifluoroalkyl carbocations of the thiophene series. These cations were studied by low-temperature NMR spectroscopy in the superacids, which shed light on their reactivity and reaction mechanisms. The cations may react with (hetero)aromatic π-nucleophiles in various directions, depending on their structures as well as the reaction temperature and time. These transformations resulted in the formation of novel fluoro-organics of the thiophene family, namely, products of arylation of both the thiophene system and its side chain, hydrodehalogenation of halothiophenes, or electrophilic "dimerization".

AB - Protonation of oxygen in the side chain of the Me3SiO group (followed by the elimination of Me3SiOH) and protonation of the thiophene ring in 2-chloro(or bromo)-5-(1′-Me3SiO-1′-trifluoromethyl-alkyl)thiophenes in Brønsted superacids (CF3SO3H, FSO3H) gave rise to short-lived and reactive trifluoroalkyl carbocations of the thiophene series. These cations were studied by low-temperature NMR spectroscopy in the superacids, which shed light on their reactivity and reaction mechanisms. The cations may react with (hetero)aromatic π-nucleophiles in various directions, depending on their structures as well as the reaction temperature and time. These transformations resulted in the formation of novel fluoro-organics of the thiophene family, namely, products of arylation of both the thiophene system and its side chain, hydrodehalogenation of halothiophenes, or electrophilic "dimerization".

KW - POLYMER SOLAR-CELLS

KW - PROTONATED HALOTHIOPHENES

KW - ELECTROPHILIC ACTIVATION

KW - TMS-ETHERS

KW - H-1-NMR

KW - ACID

UR - http://www.scopus.com/inward/record.url?scp=85084698374&partnerID=8YFLogxK

U2 - 10.1021/acs.joc.0c00170

DO - 10.1021/acs.joc.0c00170

M3 - Article

AN - SCOPUS:85084698374

VL - 85

SP - 5872

EP - 5883

JO - Journal of Organic Chemistry

JF - Journal of Organic Chemistry

SN - 0022-3263

IS - 9

ER -

ID: 69890050

Generation and NMR Study of Short-Lived and Reactive Trifluoroalkyl Carbocations of the α-Halogenothiophene Series in Brønsted Superacids: Reactions of the Cations with Arenes

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