Protonation of captodative trifluoromethylated aminoalkenes and isomerization of their salts. An <i>ab initio</i> study

Kondrashov, E. V.; Chípanina, N. N.; Aksamentova, T. N.; Rulev, Alexander Yu.

doi:10.1002/poc.1897

Cited by 5 publications

(2 citation statements)

References 29 publications

(41 reference statements)

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“…The basic centers in molecules of compounds 1 , 2 , 3 , 4 , 5 , 6 , 7 are nitrogen, oxygen, and olefinic carbon (C β for captodative 1 , 2 , 3 , 4 and C α for push–pull 5 , 6 , 7 derivatives) atoms. It was previously shown that captodative enamines containing CF 3 group are protonated by strong organic and mineral acids to give enammonium and iminium salts . The ratio of N‐protonated and C‐protonated forms depends on the nature of base and acid strength.…”

Section: Resultsmentioning

confidence: 99%

“…For this reason, different aspects of the chemistry of both captodative and push–pull aminoalkenes bearing trifluoroacetyl substituent as a strong EWG attract special attention during the last decade . In continuation of our recent research in this field, we have performed a comparative examination of basic properties of captodative and push–pull fluorine‐bearing aminoalkenes and their non‐fluorinated analogues (Table ).…”

Section: Introductionmentioning

confidence: 99%

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Basicity of the polydentate captodative aminoenones. Ab initio , DFT, and FTIR study

Kondrashov

Oznobikhina

Aksamentova

et al. 2016

J. Phys. Org. Chem.

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Electron donating ability of the oxygen, nitrogen, and carbon atoms of captodative aminoenones R'CH = C(NR 2 )EWG, EWG = CHO, C(O)Me, C(O)CF 3 , C(O)Ph was investigated using ab initio and Density Functional Theory (DFT) calculations, Natural Bond Orbital (NBO) analysis, and Fourier Transform InfraRed (FTIR) spectroscopy. The influence of both electron withdrawing group (EWG) and double bond substituents on the proton affinity of the basic centers, orbital interaction, as well as resonance stabilization energies between heteroatoms and double bonds are discussed. The results obtained are critically compared with the pushpull aminoenones. The comparison of experimental values ΔνOH and theoretical values of H-bonding energy was used to determine the H-complex type of aminoenone with phenol and the H-bond strength. a Current work. Chart 3. Unusual reactions of captodative aminoalkenes. BASICITY OF THE CAPTODATIVE AMINOENONES. AB INITIO, DFT, AND FTIR STUDY a PA are ΔH 298 values. b PCM calculations in CCl 4 (ε = 2.23) (italic). c PCM calculations in water (ε = 78.36) (bold). BASICITY OF THE CAPTODATIVE AMINOENONES. AB INITIO, DFT, AND FTIR STUDY

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Section: Resultsmentioning

confidence: 99%

Section: Introductionmentioning

confidence: 99%

Basicity of the polydentate captodative aminoenones. Ab initio , DFT, and FTIR study

Kondrashov

Oznobikhina

Aksamentova

et al. 2016

J. Phys. Org. Chem.

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Dramatic Mechanistic Change in Acid‐Catalyzed Arylation of Azafulleroids Depending on their Ambident N/C Basicity: Formation of Cyclopentene Centered Pentakisadduct

Ikuma

Doi

Fujioka

et al. 2014

Chemistry An Asian Journal

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Azafulleroid, amino-bridged [5,6]-open fullerene, has the ambident N/C basicity of the incorporated enamine moiety. Acid-catalyzed arylation of N-substituted azafulleroids proceeded via two types of initial N/C protonation to perform monoarylation or 1,4-bisarylation for the N-alkyl substituents and shuttlecock-type pentakisarylation for the N-phenyl substituent. The dramatic product change was explained by considering the possible mechanism as well as the DFT computational results.

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The structure and proton affinity of N‐benzyl‐N‐(allenyl)trifluoromethanesulfonamide: FT‐IR, DFT and ab initio study, NBO analysis

Shainyan

Chípanina

Oznobikhina

et al. 2013

J of Physical Organic Chem

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The first N-allenyl derivative of trifluoromethanesulfonamide, N-benzyl-N-(allenyl)trifluoromethanesulfonamide (1), was studied experimentally by the FT-IR spectroscopy and theoretically at the DFT and MP2 levels of theory. The intramolecular interaction of the nitrogen atom with the triflyl and the allenyl group was studied in comparison with the analogously substituted vinyl derivatives. Compound 1 in heptane solution at 295-183 K exists as an equilibrium mixture of conformational isomers. Protonation at different basic sites in a series of reference molecules is studied theoretically. The central C 2 atom of the allenyl group in 1 has the highest proton affinity, which is 16 kcal/mol higher than in the N-vinyl analogues. The relative ability of the allenyl and vinyl groups to conjugation with an electron-rich and electron-deficient nitrogen atom lone electron pair is discussed. From the NBO analysis, the conjugation of the nitrogen lone electron pair with the allenyl group is much stronger than with the vinyl group.

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Protonation of captodative trifluoromethylated aminoalkenes and isomerization of their salts. An ab initio study

Cited by 5 publications

References 29 publications

Basicity of the polydentate captodative aminoenones. Ab initio , DFT, and FTIR study

Basicity of the polydentate captodative aminoenones. Ab initio , DFT, and FTIR study

Dramatic Mechanistic Change in Acid‐Catalyzed Arylation of Azafulleroids Depending on their Ambident N/C Basicity: Formation of Cyclopentene Centered Pentakisadduct

The structure and proton affinity of N‐benzyl‐N‐(allenyl)trifluoromethanesulfonamide: FT‐IR, DFT and ab initio study, NBO analysis

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