Regioselectivity of the protonation of capto-dative enaminones

Rulev, Alexander Yu.; Zinchenko, S. V.

doi:10.1070/mc2001v011n02abeh001431

Cited by 11 publications

(8 citation statements)

References 9 publications

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“…In the authors' opinion, this fact excludes the mechanism of intramolecular proton transfer. Analogous results were obtained when captodative aminoenones were treated with a strong carboxylic acid . In contrast, intramolecular transfer of deuterium cation N → C β in N‐deuteried 2‐methyl‐1‐(β‐methylstyryl)piperidine has been proposed .…”

Section: Resultsmentioning

confidence: 69%

“…Moreover, because this reaction was carried out in CD 3 OD, an alternative mechanism including the solvent participation could be possible. Finally, experimentally observed solid‐state isomerization of some enammonium salts of classical enamines to its iminium ones and transformations of hydrochloride of captodative aminoenone to Markovnikov adduct were interpreted in terms of intramolecular rearrangement mechanism.…”

Section: Resultsmentioning

confidence: 99%

“…The results of this research have led the authors to the conclusion that N‐protonated enamines are so reactive that their isolation in pure form is extremely difficult. In fact, really stable compounds having an enammonium structure were prepared only at the protonation of captodative enamines bearing a cyano‐, carbonyl‐ or formyl group . These unusual properties of the salts are caused by restoration of effective π,π ‐conjugation of the double bond and the electron‐withdrawing geminal substituent and also the stabilizing effect of the intramolecular hydrogen bond, which is formed in N‐protonated forms …”

Section: Introductionmentioning

confidence: 99%

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

Kondrashov

Chípanina

Aksamentova

et al. 2011

J of Physical Organic Chem

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A study of the regioselectivity of protonation of captodative trifluoromethylated enamines was carried out using MP2/6‐311 + G(d,p) calculations and the natural bond orbital analysis. The central issue of this research concerns the influence of the electron‐withdrawing group, which is not capable of the π,π‐conjugation, on the properties of captodative enamines and their salts. The presence of CF3 group in such type of enamines levels the energy of their N‐protonated and C‐protonated forms. The transition states were found for both intramolecular and intermolecular processes of the proton transfer. The more possible mechanism of the isomerization of enammonium and iminium cations includes the proton transfer from N‐protonated form to olefinic carbon atom of the starting enamine. The transition state energies, which correspond to intermolecular process, are relatively low (11–13 kcal mol–1) in contrast to the intramolecular pathway (64–69 kcal mol–1). Copyright © 2011 John Wiley & Sons, Ltd.

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Section: Resultsmentioning

confidence: 69%

Section: Resultsmentioning

confidence: 99%

Section: Introductionmentioning

confidence: 99%

See 1 more Smart Citation

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

Kondrashov

Chípanina

Aksamentova

et al. 2011

J of Physical Organic Chem

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“…So, a priori , these derivatives can react with electrophiles via their nitrogen and β ‐olefinic carbon atom (as classical enamines) or carbonyl oxygen atom (as enones). In fact, the ambident nucleophilic character of the studied type of compounds was demonstrated earlier by their reactions with different acids …”

Section: Introductionmentioning

confidence: 58%

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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“…Thus the reactions of mineral or strong carboxylic acids with the aminoalkenes 2, which are activated by the geminal cyano, 184 carbonyl, 185 formyl 186,187 or azomethine group, 188 generally afford the corresponding enammonium salts 67a,c ± e. It should be emphasised that the hydrochlorides 67a,c,d (X = Cl) were isolated and completely characterised.…”

Section: Reactions With Electrophilic Reagents a Protonation And Hydr...mentioning

confidence: 99%

Captodative aminoalkenes

Rulev¹

2002

Russ. Chem. Rev.

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Regioselectivity of the protonation of capto-dative enaminones

Cited by 11 publications

References 9 publications

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

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

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

Captodative aminoalkenes

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