Oxidation of chiral 2(5H)-furanone bis-thioethers to disulfoxides

A.M. Khabibrakhmanova a*, E.S. Rabbanieva a**, D.P. Gerasimova b***, O.A. Lodochnikova a****,

L.Z. Latypova a*****, A.R. Kurbangalieva a******

aKazan Federal University, Kazan, 420008 Russia

bArbuzov Institute of Organic and Physical Chemistry, FRC Kazan Scientific Center,

Russian Academy of Sciences, Kazan, 420088 Russia

E-mail: *AMHabibrahmanova@kpfu.ru, **EnSRabbanieva@kpfu.ru, ***darya.p_gerasimova@mail.ru,

 ****lod_olga@mail.ru, *****llatypov@kpfu.ru, ******akurbang@kpfu.ru

Received December 16, 2022; Accepted February 1, 2023

 

ORIGINAL ARTICLE

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DOI: 10.26907/2542-064X.2023.1.133-148

For citation: Khabibrakhmanova A.M., Rabbanieva E.S., Gerasimova D.P., Lodochnikova O.A., Latypova L.Z., Kurbangalieva A.R. Oxidation of chiral 2(5H)-furanone bis-thioethers to disulfoxides. Uchenye Zapiski Kazanskogo Universiteta. Seriya Estestvennye Nauki, 2023, vol. 165, no. 1, pp. 133–148. doi: 10.26907/2542-064X.2023.1.133-148. (In Russian)

 

Abstract

Novel disulfinyl derivatives based on 3,4-dichloro-2(5H)-furanone, aliphatic dithiols, and monoterpene alcohols were synthesized. Chiral bis-thioethers in the molecules of which the dithiol fragment links two five-membered cycles at C4 atoms were obtained in the reactions of 5(S)-(l-menthyloxy)- and 5(S)-(l-bornyloxy)-2(5H)-furanones with ethane-1,2-dithiol and propane-1,3-dithiol in acetone in basic medium. The action of an excess of m-chloroperoxybenzoic acid (2.0–3.2 equiv.) on bis-thioethers led to the formation of the corresponding mono- and disulfoxides bearing l-menthol or l-borneol fragments at the 5th position of the lactone ring. The methods of column chromatography and fractional recrystallization were used for the isolation of individual products. The structure of the synthesized heterocycles was proved by IR and NMR spectroscopy, and their composition was confirmed by high-resolution mass spectrometry. The molecular structure of the three disulfoxides was characterized by X-ray diffraction analysis.

Keywords: 2(5H)-furanones, aliphatic dithiols, bis-thioethers, disulfoxides, optical activity, X-ray diffraction analysis

Acknowledgments. This study was supported by the Kazan Federal University Strategic Academic Leadership Program (PRIORITY-2030).

The XRD study was carried out under the state assignment to the FRC Kazan Scientific Center, Russian Academy of Sciences.

Figure Captions

Scheme 1. Oxidation reactions of bis-thioethers 1–4 to sulfoxides.

Fig. 1. 1Н NMR spectra (CDCl3, 400 MHz) of disulfoxides 7b (a) and 7c (b).

Fig. 2. Molecular geometry of disulfoxides 7b (a), 8c (b), and 9c (c) in a crystal.

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