Brominated CF3-allyl alcohols as multicentered electrophiles in TfOH promoted reactions with arenes

Anna N. Kazakova, Roman O. Iakovenko, Irina A. Boyarskaya, Alexander Yu Ivanov, Margarita S. Avdontceva, Andrei A. Zolotarev, Taras L. Panikorovsky, Galina L. Starova, Valentine G. Nenajdenko, Aleksander V. Vasilyev

Research output

12 Citations (Scopus)

Abstract

Superacidic activation of CF3-substituted allyl alcohols, bearing one or two bromine atoms at the CC double bond, with TfOH was studied. These brominated alcohols were found to behave as highly reactive multicentered electrophiles. The obtained cationic intermediates were studied by means of NMR and DFT calculations. The protonation of dibromo derivatives with TfOH resulted in cyclization to form trifluoromethylated 1H-indenes and/or indan-1-ones in yields up to 90%. The reaction of dibromosubstituted CF3-allyl alcohols with arenes in the presence of TfOH gave rise to either CF3-alkenes (formal substitution of hydroxyl with an aryl group) or CF3-indenes, depending on the nucleophilicity and bulkiness of the starting arenes. The reaction of monobrominated CF3-substituted allyl alcohols with arenes in TfOH afforded two regioisomeric CF3-alkenes, as a result of arylation of both terminal carbons of the allyl system, in yields up to 95%. The obtained brominated CF3-alkenes can be converted efficiently into trifluoromethylated allenes by treatment with KOH in ethanol in yields up to 92%.

Original languageEnglish
Pages (from-to)255-265
Number of pages11
JournalOrganic Chemistry Frontiers
Volume4
Issue number2
DOIs
Publication statusPublished - Feb 2017

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Indenes
Alkenes
Bearings (structural)
Bromine
Protonation
Cyclization
Discrete Fourier transforms
Hydroxyl Radical
Substitution reactions
Ethanol
Carbon
Chemical activation
Alcohols
Nuclear magnetic resonance
Derivatives
Atoms
allyl alcohol

Scopus subject areas

  • Organic Chemistry

Cite this

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title = "Brominated CF3-allyl alcohols as multicentered electrophiles in TfOH promoted reactions with arenes",
abstract = "Superacidic activation of CF3-substituted allyl alcohols, bearing one or two bromine atoms at the CC double bond, with TfOH was studied. These brominated alcohols were found to behave as highly reactive multicentered electrophiles. The obtained cationic intermediates were studied by means of NMR and DFT calculations. The protonation of dibromo derivatives with TfOH resulted in cyclization to form trifluoromethylated 1H-indenes and/or indan-1-ones in yields up to 90{\%}. The reaction of dibromosubstituted CF3-allyl alcohols with arenes in the presence of TfOH gave rise to either CF3-alkenes (formal substitution of hydroxyl with an aryl group) or CF3-indenes, depending on the nucleophilicity and bulkiness of the starting arenes. The reaction of monobrominated CF3-substituted allyl alcohols with arenes in TfOH afforded two regioisomeric CF3-alkenes, as a result of arylation of both terminal carbons of the allyl system, in yields up to 95{\%}. The obtained brominated CF3-alkenes can be converted efficiently into trifluoromethylated allenes by treatment with KOH in ethanol in yields up to 92{\%}.",
author = "Kazakova, {Anna N.} and Iakovenko, {Roman O.} and Boyarskaya, {Irina A.} and Ivanov, {Alexander Yu} and Avdontceva, {Margarita S.} and Zolotarev, {Andrei A.} and Panikorovsky, {Taras L.} and Starova, {Galina L.} and Nenajdenko, {Valentine G.} and Vasilyev, {Aleksander V.}",
year = "2017",
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language = "English",
volume = "4",
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Brominated CF3-allyl alcohols as multicentered electrophiles in TfOH promoted reactions with arenes. / Kazakova, Anna N.; Iakovenko, Roman O.; Boyarskaya, Irina A.; Ivanov, Alexander Yu; Avdontceva, Margarita S.; Zolotarev, Andrei A.; Panikorovsky, Taras L.; Starova, Galina L.; Nenajdenko, Valentine G.; Vasilyev, Aleksander V.

In: Organic Chemistry Frontiers, Vol. 4, No. 2, 02.2017, p. 255-265.

Research output

TY - JOUR

T1 - Brominated CF3-allyl alcohols as multicentered electrophiles in TfOH promoted reactions with arenes

AU - Kazakova, Anna N.

AU - Iakovenko, Roman O.

AU - Boyarskaya, Irina A.

AU - Ivanov, Alexander Yu

AU - Avdontceva, Margarita S.

AU - Zolotarev, Andrei A.

AU - Panikorovsky, Taras L.

AU - Starova, Galina L.

AU - Nenajdenko, Valentine G.

AU - Vasilyev, Aleksander V.

PY - 2017/2

Y1 - 2017/2

N2 - Superacidic activation of CF3-substituted allyl alcohols, bearing one or two bromine atoms at the CC double bond, with TfOH was studied. These brominated alcohols were found to behave as highly reactive multicentered electrophiles. The obtained cationic intermediates were studied by means of NMR and DFT calculations. The protonation of dibromo derivatives with TfOH resulted in cyclization to form trifluoromethylated 1H-indenes and/or indan-1-ones in yields up to 90%. The reaction of dibromosubstituted CF3-allyl alcohols with arenes in the presence of TfOH gave rise to either CF3-alkenes (formal substitution of hydroxyl with an aryl group) or CF3-indenes, depending on the nucleophilicity and bulkiness of the starting arenes. The reaction of monobrominated CF3-substituted allyl alcohols with arenes in TfOH afforded two regioisomeric CF3-alkenes, as a result of arylation of both terminal carbons of the allyl system, in yields up to 95%. The obtained brominated CF3-alkenes can be converted efficiently into trifluoromethylated allenes by treatment with KOH in ethanol in yields up to 92%.

AB - Superacidic activation of CF3-substituted allyl alcohols, bearing one or two bromine atoms at the CC double bond, with TfOH was studied. These brominated alcohols were found to behave as highly reactive multicentered electrophiles. The obtained cationic intermediates were studied by means of NMR and DFT calculations. The protonation of dibromo derivatives with TfOH resulted in cyclization to form trifluoromethylated 1H-indenes and/or indan-1-ones in yields up to 90%. The reaction of dibromosubstituted CF3-allyl alcohols with arenes in the presence of TfOH gave rise to either CF3-alkenes (formal substitution of hydroxyl with an aryl group) or CF3-indenes, depending on the nucleophilicity and bulkiness of the starting arenes. The reaction of monobrominated CF3-substituted allyl alcohols with arenes in TfOH afforded two regioisomeric CF3-alkenes, as a result of arylation of both terminal carbons of the allyl system, in yields up to 95%. The obtained brominated CF3-alkenes can be converted efficiently into trifluoromethylated allenes by treatment with KOH in ethanol in yields up to 92%.

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DO - 10.1039/c6qo00643d

M3 - Article

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SP - 255

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JO - Organic Chemistry Frontiers

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SN - 2052-4110

IS - 2

ER -