The synthesis of 1,5-diaryl-4-arylthiopyrrolidin-2-ones by arylsulfenylation of styryl acetic acid N-arylamides

N. M. Tsyzoryk, I. Yu. Danyliuk, A. I. Vaskevych, R. I. Vaskevych, M. V. Vovk

Abstract


The role of the electrophilic intramolecular cyclization (EIC) reaction of unsaturated carboxylic acid amides has been described for the design of arylthio-containing lactams and lactones. In order to identify the effect of the styryl moiety on regioselectivity of the electrophilic intramolecular cyclization process styryl acetic acid amides with electron-donating substituents in para-position of the styryl moiety have been studied. It has been found that these compounds react with phenyl and p-tolylsulfenylchlorides in nitromethane in the presence of lithium perchlorate as a “doping additive” to form 1,5-diaryl-4-arylthiopyrrolidin-2-ones with the yield of 60-66%. It is most likely that the reaction found includes the formation of the episulfonium cation stabilized by the perchlorate-anion followed by 5-endo-cyclization onto the nitrogen atom of the amide group. The structure of the compounds synthesized has been confirmed by their spectral parameters. In particular, the IR-spectra contain strong absorption bands C=O at 1703-1703 cm-1, and 1H NMR-spectra of the compounds obtained are characterized by two protons multiple shifts of the H3 pyrrolidine ring at 2.52-2.64 and 3.08-3.22 ppm, respectively, H4 proton multiple shifts at 3.61-3.76 ppm and H5 at 4.99-5.09 ppm. Formation of the pyrrolidine ring as a result of cyclization has been reliably proven by 13C NMR-spectra with the typical signals of carbon atoms: C3 (37 ppm), C4 (48 ppm), C5 (69 ppm) and C2 (172 ppm).


Keywords


styryl acetic acid amides; electrophilic intramolecular cyclization; arylsulfenyl chlorides; pyrrolidin-2-ones

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References


Seki M., Yamanaka T., Kondo K. J. Org. Chem., 2000, Vol. 65, pp.517-522.

Kobayashi S., Kobayashi K., Hirai K. Synlett, 1999, pp.909-912.

Joie C., Deckers K., Enders P. Synthesis, 2014, Vol. 46, pp.799-808.

Pelletier S. M.-C., Ray P. C., Dixon D. J. Org. Let., 2009, Vol. 11, pp.4512-4515.

Anderson J. C., Horsfall L. R., Kalogirou A. S., Mills M. R., Stepney G. J., Tizzard G. J. J. Org. Chem., 2012, Vol. 77, pp.6186-6198.

Heinrich D. M., Flanagan J. U., Jamieson S. M. F., Silva S., Rigoreay L. J., Trivier E., Raynkom T., Turnbull A. P., Penny W. A. Eur. J. Med. Chem. 2013, Vol. 62, pp.738-744.

Tsizorik N. M., Vaskevich A. I., Rusanov E. B., Staninets V. I., Vovk M. V. Russ. J. Org. Chem., 2011, Vol. 47, pp.1146-1152.

Tsizorik N. M., Vaskevich A. I., Rusanov E. B., Staninets V. I., Vovk M. V. Russ. J. Org. Chem., 2012, Vol. 48, pp.193-201.

Tsizorik N. M., Vaskevich A. I., Rusanov E. B., Rozhenko A. B., Vovk M. V. Russ. J. Org. Chem., 2014, Vol. 50, pp.1397-1408.

Tsizorik N. M., Vaskevich A. I., Staninets V. I., Rusanov E. B., Vovk M. V. Russ. J. Org. Chem., 2012, Vol. 48, pp.1536-1543.

Zefirov N. S., Smith V. A., Bodrikov I. V., Krimer M. Z. Doklady Akademii Nauk SSSR, 1978, Vol. 240, pp.858-860.

Krimer M. Z., Smith B. A., Shamshurin A. A. Doklady Akademii Nauk SSSR, 1973, Vol. 209, pp.866-866.

Tsizorik N. M., Vaskevich A. I., Vaskevich R. I., Vovk M. V. Russ. J. Org. Chem., 2015, Vol. 51, p.226.

Vaskevich A. I., Tsizorik N. M., Staninets V. I., Rusanov E. B., Vovk M. V. Russ. J. Org. Chem., 2012, Vol. 48, p.1536.


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DOI: https://doi.org/10.24959/ophcj.15.870

Abbreviated key title: Ž. org. farm. hìm.

ISSN 2518-1548 (Online), ISSN 2308-8303 (Print)