Reactions of Trifluoroacetyl Alkynes Under Electrophilic Activation with Brønsted Acids or Acidic Zeolites

Selbi K. Nursahedova, Dmitry S. Ryabukhin, Vasily M. Muzalevskiy, Roman O. Iakovenko, Irina A. Boyarskaya, Galina L. Starova, Valentine G. Nenajdenko, Aleksander V. Vasilyev

Research output

Abstract

The reaction of trifluoroacetyl alkynes [ArC≡C(C=O)CF 3 ] with H 2 SO 4 or TfOH affords products of addition of the acids to the acetylene bond. Hydrolysis of these adducts results in the formation of the corresponding 1,3-diketones existing in form of enols [Ar(HO)C=CH(C=O)CF 3 ] in up to 98 % yield. The application of less acidic TfOH-pyridine system permits transformation of these alkynes into the corresponding vinyl triflates in up to 76 % yield. Moreover, this reaction is totally stereoselective to give only Z-configured vinyl triflates. The reaction of trifluoroacetyl alkynes with arenes in TfOH or under the action of acidic HUSY zeolites CBV-720 gives rise to 1,3-diaryl-1-CF 3 -indenes in up to 81 % yield. Electronic characteristics of initial intermediate mono- and dicationic species derived from such alkynes in the highly acidic media were studied by DFT calculations. Plausible cationic reaction mechanism was proposed.

Original languageEnglish
Pages (from-to)1293-1300
Number of pages8
JournalEuropean Journal of Organic Chemistry
Volume2019
Issue number6
DOIs
Publication statusPublished - 14 Feb 2019

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Zeolites
Alkynes
alkynes
zeolites
Chemical activation
activation
acids
Acids
Indenes
indene
Acetylene
Discrete Fourier transforms
acetylene
adducts
hydrolysis
Hydrolysis
pyridines
methylidyne
products
electronics

Scopus subject areas

  • Physical and Theoretical Chemistry
  • Organic Chemistry

Cite this

Nursahedova, Selbi K. ; Ryabukhin, Dmitry S. ; Muzalevskiy, Vasily M. ; Iakovenko, Roman O. ; Boyarskaya, Irina A. ; Starova, Galina L. ; Nenajdenko, Valentine G. ; Vasilyev, Aleksander V. / Reactions of Trifluoroacetyl Alkynes Under Electrophilic Activation with Brønsted Acids or Acidic Zeolites. In: European Journal of Organic Chemistry. 2019 ; Vol. 2019, No. 6. pp. 1293-1300.
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abstract = "The reaction of trifluoroacetyl alkynes [ArC≡C(C=O)CF 3 ] with H 2 SO 4 or TfOH affords products of addition of the acids to the acetylene bond. Hydrolysis of these adducts results in the formation of the corresponding 1,3-diketones existing in form of enols [Ar(HO)C=CH(C=O)CF 3 ] in up to 98 {\%} yield. The application of less acidic TfOH-pyridine system permits transformation of these alkynes into the corresponding vinyl triflates in up to 76 {\%} yield. Moreover, this reaction is totally stereoselective to give only Z-configured vinyl triflates. The reaction of trifluoroacetyl alkynes with arenes in TfOH or under the action of acidic HUSY zeolites CBV-720 gives rise to 1,3-diaryl-1-CF 3 -indenes in up to 81 {\%} yield. Electronic characteristics of initial intermediate mono- and dicationic species derived from such alkynes in the highly acidic media were studied by DFT calculations. Plausible cationic reaction mechanism was proposed.",
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author = "Nursahedova, {Selbi K.} and Ryabukhin, {Dmitry S.} and Muzalevskiy, {Vasily M.} and Iakovenko, {Roman O.} and Boyarskaya, {Irina A.} and Starova, {Galina L.} and Nenajdenko, {Valentine G.} and Vasilyev, {Aleksander V.}",
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Reactions of Trifluoroacetyl Alkynes Under Electrophilic Activation with Brønsted Acids or Acidic Zeolites. / Nursahedova, Selbi K.; Ryabukhin, Dmitry S.; Muzalevskiy, Vasily M.; Iakovenko, Roman O.; Boyarskaya, Irina A.; Starova, Galina L.; Nenajdenko, Valentine G.; Vasilyev, Aleksander V.

In: European Journal of Organic Chemistry, Vol. 2019, No. 6, 14.02.2019, p. 1293-1300.

Research output

TY - JOUR

T1 - Reactions of Trifluoroacetyl Alkynes Under Electrophilic Activation with Brønsted Acids or Acidic Zeolites

AU - Nursahedova, Selbi K.

AU - Ryabukhin, Dmitry S.

AU - Muzalevskiy, Vasily M.

AU - Iakovenko, Roman O.

AU - Boyarskaya, Irina A.

AU - Starova, Galina L.

AU - Nenajdenko, Valentine G.

AU - Vasilyev, Aleksander V.

PY - 2019/2/14

Y1 - 2019/2/14

N2 - The reaction of trifluoroacetyl alkynes [ArC≡C(C=O)CF 3 ] with H 2 SO 4 or TfOH affords products of addition of the acids to the acetylene bond. Hydrolysis of these adducts results in the formation of the corresponding 1,3-diketones existing in form of enols [Ar(HO)C=CH(C=O)CF 3 ] in up to 98 % yield. The application of less acidic TfOH-pyridine system permits transformation of these alkynes into the corresponding vinyl triflates in up to 76 % yield. Moreover, this reaction is totally stereoselective to give only Z-configured vinyl triflates. The reaction of trifluoroacetyl alkynes with arenes in TfOH or under the action of acidic HUSY zeolites CBV-720 gives rise to 1,3-diaryl-1-CF 3 -indenes in up to 81 % yield. Electronic characteristics of initial intermediate mono- and dicationic species derived from such alkynes in the highly acidic media were studied by DFT calculations. Plausible cationic reaction mechanism was proposed.

AB - The reaction of trifluoroacetyl alkynes [ArC≡C(C=O)CF 3 ] with H 2 SO 4 or TfOH affords products of addition of the acids to the acetylene bond. Hydrolysis of these adducts results in the formation of the corresponding 1,3-diketones existing in form of enols [Ar(HO)C=CH(C=O)CF 3 ] in up to 98 % yield. The application of less acidic TfOH-pyridine system permits transformation of these alkynes into the corresponding vinyl triflates in up to 76 % yield. Moreover, this reaction is totally stereoselective to give only Z-configured vinyl triflates. The reaction of trifluoroacetyl alkynes with arenes in TfOH or under the action of acidic HUSY zeolites CBV-720 gives rise to 1,3-diaryl-1-CF 3 -indenes in up to 81 % yield. Electronic characteristics of initial intermediate mono- and dicationic species derived from such alkynes in the highly acidic media were studied by DFT calculations. Plausible cationic reaction mechanism was proposed.

KW - Alkynes

KW - Electrophilic addition, Aromatic substitution

KW - Protonation

KW - Trifluoromethyl group

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