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Article

Efficient Regioselective Synthesis of Novel Ensembles of Organylselanyl-Functionalized Divinyl Sulfides and 1,3-Thiaselenoles under Phase Transfer Catalysis Conditions

by
Andrey S. Filippov
,
Svetlana V. Amosova
,
Nataliya A. Makhaeva
,
Alexander I. Albanov
* and
Vladimir A. Potapov
A. E. Favorsky Irkutsk Institute of Chemistry, Siberian Division of the Russian Academy of Sciences, 1 Favorsky Str., Irkutsk 664033, Russia
*
Author to whom correspondence should be addressed.
Catalysts 2023, 13(8), 1227; https://doi.org/10.3390/catal13081227
Submission received: 1 July 2023 / Revised: 9 August 2023 / Accepted: 18 August 2023 / Published: 21 August 2023
(This article belongs to the Special Issue Recent Advances in Catalytic Synthesis and Application of Heterocyclic and Heteroatom Compounds)
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Abstract

:
Efficient regioselective synthesis of novel ensembles of organylselanyl-functionalized 1,3-thiaselenoles and divinyl sulfides in high yields under phase transfer catalysis conditions was developed. The methodology is based on the generation of sodium [(Z)-2-(vinylsulfanyl)ethenyl]selenolate and 1,3-thiaselenol-2-ylmethylselenolate, which were involved in a nucleophilic addition reaction with activated alkenes such as acrylonitrile, acrylamide, methyl vinyl ketone, methyl, and ethyl acrylates. In the case of methyl vinyl ketone, the reaction was accompanied by the hydrogenation of the carbonyl group. Methylene chloride was involved in the nucleophilic substitution reaction with sodium [(Z)-2-(vinylsulfanyl)ethenyl]selenolate and 1,3-thiaselenol-2-ylmethylselenolate to afford new polyunsaturated compounds with several sulfur and selenium atoms.

1. Introduction

Selenium had previously been considered a poison for many years until Schwartz and Foltz found that this element is an important micronutrient for humans and animals [1]. Since then, interest in the chemistry of organoselenium compounds has sharply increased, and multifaceted studies of these compounds gave impetus to the development of bioorganic chemistry, enzymology, and medicine [2,3,4,5,6,7].
To date, many classes of organoselenium compounds have been studied, and promising products, especially selenium heterocycles, have been found that exhibit various kinds of biological activities [8,9,10,11,12,13,14,15,16,17,18,19,20,21,22,23] including antiviral [13,14], antibacterial [11,12], antitumor [8,9,10,11], and glutathione peroxidase-like properties [15,16,17].
Ebselen (2-phenyl-1,2-benzoselenazol-3(2H)-one) is a well-known selenium-containing heterocyclic compound, an anti-inflammatory drug with neuroprotective and glutathione peroxidase-like properties [23,24,25]. Ebselen can be used for the prevention and treatment of cardiovascular diseases including ischemic stroke and reperfusion injury. It is worth noting that ebselen was found to inhibit SARS-CoV2 viral replication [24,25]. Recently, this compound has been undergoing evaluation as a therapeutic agent in clinical trials in the treatment of COVID-19, Meniere’s disease, hearing loss, and bipolar disorder [23].
Other important classes of selenium heterocycles are 1,3-diselenoles and 1,3-thiaselenoles derivatives. The structures of 1,3-diselenole or 1,3-thiaselenole scaffolds are included in diselenafulvenes, thiaselenafulvenes, tetraselenafulvalenes, and dithiadiselenafulvalenes. Tetraselenafulvalenes and dithiadiselenafulvalenes are used as electron donors for the preparation of various conducting materials such as semiconductors, organic metals, superconductors, ferromagnets, and organic Dirac materials [26,27,28,29,30,31,32,33,34,35,36]. These materials can find augmenting applications in various areas. The synthesis of tetraselenafulvalenes and dithiadiselenafulvalenes is usually based on 1,3-diselenole and 1,3-thiaselenole derivatives [32,33,34,35,36,37].
A number of 1,3-thiaselenole derivatives, dithiadiselenafulvalenes, are found to be promising electron donors for the preparation of conducting materials (Figure 1) [38,39,40,41]. For example, a charge transfer complex of 1,4,5-triselena-8-thiafulvalene with tetracyanoquinodimethane exhibited high anisotropic conductivity in the polycrystalline sample [38].
Organylselanyl-functionalized divinyl sulfides are very rare compounds. However, divinyl sulfides, and especially the first representative of this series, unsubstituted divinyl sulfide, are promising starting compounds for the synthesis of polyfunctional sulfides and heterocycles [42]. Divinyl sulfide exhibits very useful properties as a highly reactive monomer for the preparation of various valuable polymeric materials by polymerization and copolymerization reactions, as well as an effective crosslinking agent (Figure 1) [42].
Functionalized divinyl sulfides and (4-tert-butylcyclohexylidene)methyl styryl sulfides, show antioxidant, antinociceptive, and glutathione peroxidase-like properties (Figure 1) [43,44]. The potential of vinyl sulfides with respect to biological activity can be demonstrated by the example of a cyclic peptide with the vinyl sulfide group (Figure 1), which is an angiotensin II analog, exhibiting high affinity and agonist activity at the AT1 receptor [45].
Earlier, we developed the efficient one-pot synthesis of 2-bromomethyl-1,3-thiaselenole in high yield from selenium dibromide with divinyl sulfide [46]. 2-Bromomethyl-1,3-thiaselenole is a unique reagent for organic synthesis, which exhibits unusual behavior in nucleophilic substitution reactions [46,47,48]. The bromine atom in 2-bromomethyl-1,3-thiaselenole is highly activated by the strong anchimeric assistance effect of the selenium atom [49]. Quantum chemical calculations show that this reagent exists in equilibrium with corresponding three-membered seleniranium cation and nucleophilic reactions that proceed at three different centers of the seleniranium intermediate [46].
New promising reagents, namely, 1,2-bis[(Z)-2-(vinylsulfanyl)ethenyl] diselenide (1) and 1,3-thiaselenol-2-ylmethyl selenocyanate (2), were obtained based on 2-bromomethyl-1,3-thiaselenole. The reaction of 2-(bromomethyl)-1,3-thiaselenole with sodium ethanethiolate in acetonitrile at room temperature afforded diselenide 1 in 82% yield (Scheme 1) [47].
The reaction of 2-bromomethyl-1,3-thiaselenole with potassium selenocyanate proceeded very smoothly (acetonitrile, room temperature, 5 min) giving selenocyanate 2 in a quantitative yield (Scheme 1) [48].
Compounds 1 and 2 were used as starting materials for the development of efficient synthetic methods for the preparation of novel ensembles of unsaturated sulfur/selenium products.

2. Results and Discussion

A goal of this work is to develop efficient regioselective syntheses of novel families of organylselanyl-functionalized 1,3-thiaselenoles and divinyl sulfides based on addition reactions of sodium [(Z)-2-(vinylsulfanyl)ethenyl]selenolate and 1,3-thiaselenol-2-ylmethylselenolate, generated from compounds 1 and 2, to activated alkenes (Scheme 2).
The treatment of compounds 1 and 2 with sodium borohydride (NaBH4) led to the generation of corresponding sodium selenolates, which were involved in the nucleophilic addition reaction with activated alkenes such as acrylonitrile, methyl and ethyl acrylates, acrylamide, and methyl vinyl ketone.
We found that phase transfer catalysis conditions using triethylbenzylammonium chloride (TEBAC) as a phase transfer catalyst made it possible to realize this addition reaction in a chemo- and regioselective fashion and obtain the target products in high yields. The reactions were carried out by adding an aqueous solution of NaBH4 to a solution of compounds 1 or 2 in methylene chloride or chloroform under argon followed by stirring for 1–3 h at room temperature.
The reaction of selenocyanate 2 with activated alkenes (acrylonitrile, methyl and ethyl acrylates, acrylamide, and methyl vinyl ketone) was carried out in the two-phase system NaBH4/H2O/TEBAC/chloroform under argon with stirring at room temperature for 3 h (Scheme 3).
3-[(1,3-Thiaselenol-2-ylmethyl)selanyl]propanenitrile (3a) was obtained in 99% yield and did not require additional purification (Scheme 3).
Methyl and ethyl acrylates and acrylamide were involved in the reaction with compound 2 affording the corresponding addition products 3b,c,d in 93%, 95%, and 93% yields, respectively (Scheme 3).
When methyl vinyl ketone was used as an activated alkene in the reaction with compound 2 in the two-phase system NaBH4/H2O/TEBAC/chloroform, the suggested product was not obtained. In this case, the reaction was accompanied by hydrogenation of the carbonyl group affording 3-[(1,3-thiaselenol-2-ylmethyl)selanyl]butan-2-ol (3e) in 91% yield (Scheme 3).
In order to find out whether the hydrogenation would occur in another solvent, chloroform was replaced with methylene chloride. The reaction of compound 2 with methyl vinyl ketone under similar conditions in methylene chloride gave, along with hydrogenated product 3e (yield 59%), a very interesting compound 4, containing four selenium atoms, in 25% yield (Scheme 4).
Compound 4 is formed by the nucleophilic substitution of two chlorine atoms in methylene chloride with sodium 1,3-thiaselenol-2-ylmethylselenolate. The formation of the nucleophilic substitution products with chloroform was not observed in the system NaBH4/H2O/TEBAC/chloroform (Scheme 3). The ease of product formation by the nucleophilic substitution of two chlorine atoms in methylene chloride with selenium-centered nucleophiles was noted in the literature [50].
Compound 4 is a symmetrical molecule, which has two asymmetric carbon centers in the cycles. It consists of two diastereomers, which manifest themselves in the NMR spectra. For example, two signals of the selenium atom in the ring were observed in the 77Se NMR spectrum of this compound (Scheme 4).
The reaction of polyunsaturated diselenide 1 with activated alkenes in the system NaBH4/H2O/TEBAC/chloroform was studied. The reaction of diselenide 1 with methyl and ethyl acrylates and acrylamide afforded the addition of products 5a,b in 83–85% yields taking into account that one molecule of diselenide 1 gives two molecules of the target products (Scheme 5).
In the case of using methyl vinyl ketone as an activated alkene in the reaction with diselenide 1, the suggested addition product was not obtained. As in the reaction with compound 2 (Scheme 3), the process was accompanied by hydrogenation of the carbonyl group of methyl vinyl ketone, leading to 4-{[(Z)-2-(vinylsulfanyl)ethenyl]selanyl}-2-butanol (5c) in 87% yield (Scheme 5).
Acrylonitrile was involved in the reaction with diselenide 1, giving two isomers, (Z)- and (E)-3-{[2-(vinylsulfanyl)ethenyl]selanyl}propanenitriles 6a,b in 36% and 23% yields, respectively (Scheme 6).
Under the same conditions, the reaction of sodium [(Z)-2-(vinylsulfanyl)ethenyl]selenolate and 1,3-thiaselenol-2-ylmethylselenolate with divinyl sulfone led to a complex mixture containing ethyl vinyl sulfone as the major product. The possibility of the hydrogenation reaction of divinyl sulfone to ethyl vinyl sulfone under the action of NaBH4 under phase transfer catalysis conditions was confirmed by an additional experiment.
When methylene chloride was used instead of chloroform in the reaction of diselenide 1 with methyl vinyl ketone under similar conditions, three compounds 5c, 7, and 8 were obtained in 41%, 9%, and 24% yields, respectively (Scheme 7).
The formation of compounds 7 and 8 can be considered as the result of nucleophilic substitution of one or two chlorine atoms in methylene chloride by sodium [(Z)-2-(vinylsulfanyl)ethenyl]selenolate. Taking into account the formation of bis(selanyl)methane compounds 4 and 8 from methylene chloride, we suggest that this method can be used for the preparation of other bis(organylselanyl)methane derivatives by the reactions of organylselenolate anions with methylene chloride under phase transfer catalysis conditions.
We have shown the possibility of obtaining other 3-hydroxybutyl selenides from methyl vinyl ketone by this method using diphenyl diselenide as an example. When diphenyl diselenide was involved in the reaction with methyl vinyl ketone under the same conditions as the reaction of diselenide 1 (Scheme 5), 3-hydroxybutyl phenyl selenide was obtained with an 81% yield (Scheme 8).
It should be noted that alkyl and aryl 3-hydroxybutyl selenides are rare compounds, and only butyl and phenyl 3-hydroxybutyl selenides have been previously obtained [51,52,53,54]. Butyl and phenyl 3-hydroxybutyl selenides were synthesized in three stages starting from poly-3-hydroxybutanoate in 37% and 42% overall yields, respectively [51]. The proposed method (Scheme 5 and Scheme 8) makes it possible to obtain the target product (e.g., 3-hydroxybutyl phenyl selenide) in higher yield by a single-stage procedure.
Hydroxyorganyl selenides are a very important family of organoselenium compounds, many of which exhibit glutathione peroxidase mimetic properties and also serve as intermediates for organic synthesis [55,56,57,58]. For example, a novel cyclic seleninate ester with high glutathione peroxidase-like activity was obtained from allyl 3-hydroxypropyl selenide [56].
It is worth noting that the nucleophilic addition reactions of sodium [(Z)-2-(vinylsulfanyl)ethenyl]selenolate and 1,3-thiaselenol-2-ylmethylselenolate to the activated alkenes acrylonitrile, acrylamide, methyl vinyl ketone, methyl, and ethyl acrylates proceed in a regioselective fashion exclusively at the terminal carbon atom of the double bond.
The structural assignment of the obtained compounds was carried out based on the NMR investigations and mass spectrometry data and confirmed by elemental analysis. Molecular ions were observed in the mass spectra of the obtained compounds.

3. Materials and Methods

3.1. General Information

The 1H (400.1 MHz), 13C (100.6 MHz), and 77Se (76.3 MHz) NMR spectra (the spectra can be found in Supplementary Materials) were recorded on a Bruker DPX-400 spectrometer (Bruker BioSpin GmbH, Rheinstetten, Germany) in CDCl3 solutions and referred to the residual solvent peaks (CDCl3, δ = 7.27 and 77.0 ppm for 1H- and 13C-NMR, respectively), and dimethyl selenide (77Se).
Mass spectra were recorded on a Shimadzu GCMS-QP5050A (Shimadzu Corporation, Kyoto, Japan) with electron impact (EI) ionization (70 eV). The data of mass spectra are given in the experimental part regarding the maximum isotope of selenium (80Se).
Elemental analysis was performed on a Thermo Scientific Flash 2000 Elemental Analyzer (Thermo Fisher Scientific Inc., Milan, Italy). Distilled organic solvents and degassed water were used in syntheses. The spectral characteristics of obtained 3-hydroxybutyl phenyl selenide correspond to the data of the known sample [51].

3.2. Synthesis of the Products

3-[(1,3-Thiaselenol-2-ylmethyl)selanyl]propanenitrile (3a). A solution of NaBH4 (0.08 g (2.1 mmol) and TEBAC (0.005 g) in water (0.5 mL) was added to a solution of 1,3-thiaselenol-2-ylmethylselenocyanate (0.165 g, 0.61 mmol) and acrylonitrile (0.033 g (0.61 mmol) in chloroform (2 mL) under argon. The resulting mixture was stirred at room temperature for 3 h. Chloroform (5 mL) was added, and the mixture was stirred for 10 min. The organic layer was separated and dried over Na2SO4, and the solvent was removed under reduced pressure to give the product (0.18 g, 99% yield) as a light-yellow oil.
1H NMR (400 MHz, CDCl3): 2.78 (t, 2H, CH2CN, 3J 6.9 Hz), 2.91 (t, 2H, CH2CH2CN, 3J 6.9 Hz), 3.06 (dd, 1H, CH2SeCH2CH2, 3J 7.5 Hz, 2J 13.0 Hz), 3.18 (dd, 1H, CH2SeCH2CH2, 3J 8.1 Hz, 2J 13.0 Hz), 5.03 (t, 1H, SeCHS, 3J 7.7 Hz, 2JSeH 23.8 Hz), 6.41 (d, 1H, =CHS, 3J 6.2 Hz), 6.63 (d, 1H, =CHS, 3J 6.2 Hz, 2JSeH 47.5 Hz).
13C NMR (100 MHz, CDCl3): δ 18.89 (CH2SeCH2CH2, 1JSeC 70.7 Hz), 19.84 (CH2CN), 34.46 (CH2SeCH2CH2, 1JSeC 66.6 Hz), 48.15 (SeCHS, 1JSeC 68.1 Hz), 113.36 (=CHSe, 1JSeC 106.5 Hz), 118.50 (CN), 119.36 (=CHS).
77Se NMR (76 MHz, CDCl3): 233.82, 530.76 (in cycle).
MS (EI), m/z (%): 299 (7) [M]+, 165 (5), 151 (100), 107 (5), 85 (25).
Anal. Calcd for C7H9NSSe2 (297.14): C 28.29; H 3.05; N 4.71; S 10.79; Se 53.16%. Found: C 28.21; H 3.12; S 10.98; Se 53.46%.
Methyl 3-[(1,3-thiaselenol-2-ylmethyl)selanyl]propanoate (3b). Yield: 93%, a light-yellow oil. The product was purified by column chromatography (silica gel 60, 70–230 mesh, eluent: hexane, then chloroform–hexane 1:3).
1H NMR (400 MHz, CDCl3): δ 2.71 (t, 2H, CH2SeCH2CH2, 3J 6.9 Hz), 2.85 (t, 2H, CH2C(O), 3J 6.9 Hz), 2.95 (dd, 1H, CH2SeCH2CH2, 3J 7.7 Hz, 2J 12.8 Hz), 3.06 (dd, 1H, CH2SeCH2CH2, 3J 7.7 Hz, 2J 12.8 Hz), 3.67 (s, 3H, CH3), 5.00 (dd, 1H, SeCHS, 3J 7.7 Hz, 3J 8.0 Hz, 2JSeH 20.0 Hz), 6.38 (d, 1H, =CHS, 3J 6.2 Hz), 6.59 (d, 1H, =CHS, 3J 6.2 Hz, 2JSeH 48.2 Hz).
13C NMR (100 MHz, CDCl3): δ 18.71 (CH2SeCH2CH2, 1JSeC 62.7 Hz), 34.10 (CH2SeCH2CH2, 1JSeC 67.5 Hz), 35.46 (CH2C(O)), 48.22 (SeCHS, 1JSeC 65.5 Hz), 51.68 (CH3), 113.16 (=CHSe, 1JSeC 106.5 Hz), 119.35 (=CHS), 172.25 (CH2C(O)).
77Se NMR (76 MHz, CDCl3): 221.24, 528.69 (in cycle).
MS (EI), m/z (%): 332 (6) [M]+, 165 (28), 151 (100), 125 (31), 85 (52). Anal. Calcd for C8H12O2SSe2 (330.17): C 29.10; H 3.66; S 9.71; Se 47.83%. Found: C 29.31; H 3.64; S 10.01; Se 48.03%.
Ethyl 3-[(1,3-thiaselenol-2-ylmethyl)seleno]propanoate (3c). Yield: 95%, a light-yellow oil. The product was purified by column chromatography (silica gel 60, 70–230 mesh, eluent: hexane, then chloroform–hexane 1:4).
1H NMR (400 MHz, CDCl3): δ 1.27 (t, 3H, CH3, 3J 7.0 Hz), 2.65 (t, 2H, CH2SeCH2CH2, 3J 6.9 Hz), 2.83 (t, 2H, CH2C(O), 3J 6.9 Hz), 2.94 (dd, 1H, CH2SeCH2CH2, 3J 7.8 Hz, 2J 12.8 Hz), 3.05 (dd, 1H, CH2SeCH2CH2, 3J 8.0 Hz, 2J 12.8 Hz), 4.12 (q, 2H, CH2C(O), 3J 7.0 Hz), 5.00 (dd, 1H, SeCHS, 3J 7.7 Hz, 3J 8.0 Hz, 2JSeH 20.4 Hz), 6.35 (d, 1H, =CHS, 3J 5.9 Hz), 6.54 (d, 1H, =CHS, 3J 5.9 Hz, 2JSeH 47.6 Hz).
13C NMR (100 MHz, CDCl3): δ 14.16 (CH3), 18.86 (CH2SeCH2CH2, 1JSeC 64.5 Hz), 34.19 (CH2SeCH2CH2, 1JSeC 67.3 Hz), 35.81 (CH2C(O)), 48.32 (SeCHS, 1JSeC 65.5 Hz), 60.66 (CH2CH3), 113.19 (=CHSe, 1JSeC 106.9 Hz), 119.45 (=CHS), 171.91 (CH2C(O)).
77Se NMR (76 MHz, CDCl3): 219.92, 528.02 (in cycle).
MS (EI), m/z (%): 346 (30) [M]+, 165 (30), 151 (10), 125 (31), 85 (100).
Anal. Calcd for C9H14O2SSe2 (344.19): C 31.41; H 4.10; S 9.32; Se 45.88%. Found: C 31.28; H 3.98; S 9.61; Se 45.59%.
3-[(1,3-Thiaselenol-2-ylmethyl)selanyl]propanamide (3d). Yield: 93%, a light-yellow oil. The product was purified by column chromatography (silica gel 60, 70–230 mesh, eluent: hexane, then chloroform–hexane 1:3).
1H NMR (400 MHz, d6-DMSO): δ 2.45 (t, 2H, CH2C(O), 3J 7.0 Hz), 2.78 (t, 2H, CH2SeCH2CH2, 3J 7.0 Hz), 2.90 (dd, 1H, CH2SeCH2CH2, 3J 7.4 Hz, 2J 12.7 Hz), 2.99 (dd, 1H, CH2SeCH2CH2, 3J 8.0 Hz, 2J 12.7 Hz), 5.18 (dd, 1H, SeCHS, 3J 7.4 Hz, 3J 8.0 Hz), 6.53 (d, 1H, =CHS, 3J 6.2 Hz), 6.74 (d, 1H, =CHS, 3J 6.2 Hz, 2JSeH 54.4 Hz), 6.80 (br s, 1H, NH2), 7.30 (br s, 1H, NH2).
13C NMR (100 MHz, d6-DMSO): δ 19.27 (CH2SeCH2CH2, 1JSeC 62.3 Hz), 33.66 (1JSeC = 66.4, CH2SeCH2CH2), 36.51 (CH2C(O)), 47.98 (SeCHS, 1JSeC 67.1 Hz), 113.76 (=CHSe, 1JSeC 106.4 Hz), 119.32 (=CHS), 172.85 (CH2C(O)).
77Se NMR (76 MHz, d6-DMSO): 213.47, 525.27 (in cycle).
MS (EI), m/z (%): 317 (7) [M]+, 165 (5), 151 (100), 107 (5), 85 (25). Anal. Calcd for C7H11NOSSe2 (315.15): C 26.68; H 3.52; N 4.44; S 10.17; Se 50.11.%. Found: C 26.38; H 3.58; S 10.33; Se 50.15%.
4-[(1,3-Thiaselenol-2-ylmethyl)selanyl]butan-2-ol (3e). Yield: 91%, a light-yellow oil. The product was purified by column chromatography (silica gel 60, 70–230 mesh, eluent: hexane, then chloroform–hexane 1:2).
1H NMR (400 MHz, CDCl3): δ 1.21 (d, 3H, CH3, 3J 6.2 Hz), 1.76 (br s, 1H, OH), 1.80 (m, 2H, CH2CH(O)), 2.76 (dt, 2H, CH2SeCH2CH2, 2J 11.9 Hz, 3J 7.7 Hz), 2.96 (dd, 1H, CH2SeCH2CH2, 2J 12.9 Hz, 3J 8.0 Hz, 5J 1.6 Hz), 3.07 (dd, 1H, CH2SeCH2CH2, 2J 12.9 Hz, 3J 8.0 Hz, 5J 1.6 Hz), 3.90 (t. q, 1H, CH(OH)CH3, 2J 6.5 Hz, 2J 6.2 Hz), 5.04 (t, 1H, SCHSe, 3J 8.0 Hz), 6.40 (d, 1H, =CHS, 3J 6.3 Hz, 5J 1.6 Hz), 6.61 (d, 1H, =CHSe, 3J 6.3 Hz, 5J 1.6 Hz, 2JSeH 48.4 Hz ).
13C NMR (100 MHz, CDCl3): δ 21.36 (CH3), 23.47 (CH2SeCH2CH2, 1JSeC 65.2 Hz), 33.86 (CH2SeCH2CH2, 1JSeC 67.2 Hz), 39.48 (CH2C(OH)), 48.38, (SeCHS, 1JSeC 65.5 Hz), 67.51 (CH(OH)CH3), 113.23 (=CHSe, 1JSeC 106.9 Hz), 119.49 (=CHS).
77Se NMR (76 MHz, CDCl3): 198.36, 198.60; 528.79, 528.84 (in cycle).
MS (EI), m/z (%): 318 (12) [M]+, 165 (28), 151 (100), 125 (5), 85 (30).
Anal. Calcd for C8H14OSSe2 (316.18): C 30.39; H 4.46; S 10.14; Se 49.95%. Found: C 30.51; H 4.64; S 10.04; Se 50.14%.
2,2′-[Methylenebis(selenomethylene)]bis-1,3-thiaselenole (4). A solution of NaBH4 (0.085 g, 2.24 mmol) and TEBAC (0.003 g) in water (0.5 mL) was added to a solution of 1,3-thiaselenol-2-ylmethylselenocyanate (0.326 g, 1.21 mmol) and methyl vinyl ketone (0.085 g (1.21 mmol) in methylene chloride (1 mL) under argon. The resulting mixture was stirred at room temperature for 3 h. Methylene chloride (5 mL) was added, and the mixture was stirred for 10 min. The organic layer was separated and dried over Na2SO4, and the solvent was removed under reduced pressure. The residue was subjected to column chromatography (silica gel 60, 70–230 mesh, eluent: hexane, then chloroform–hexane 1:3) to give butanol 3e (0.259 g, 59% yield) and the product 4 (0.075 g, 25% yield) as light-yellow oils.
1H NMR (400 MHz, CDCl3 3.11 (dd, 1H, CH2SeCH2CH2, 3J 8.0 Hz, 2J 12.8 Hz), 3.22 (dd, 1H, CH2SeCH2CH2, 3J 8.0 Hz, 2J 12.8 Hz), 3.90 (s, 2H, CH2SeCH2SeCH2), 5.13 (t, 1H, SeCHS, 3J 8.0 Hz), 6.42 (d, 1H, =CHS, 3J 6.4 Hz), 6.63 (d, 1H, =CHS, 3J 6.4 Hz, 2JSeH 48.3 Hz).
13C NMR (100 MHz, CDCl3): δ 15.81 (CH2SeCH2SeCH2, 1JSeC 86.1 Hz), 35.61 (CH2SeCH2SeCH2, 1JSeC 67.8 Hz), 47.97 (SeCHS, 1JSeC 67.4 Hz), 113.36 (=CHSe, 1JSeC 106.3 Hz), 119.51 (=CHS).
77Se NMR (76 MHz, CDCl3): 245.83; 529.17, 529.25 (in cycle).
MS (EI), m/z (%): 502 (9) [M]+, 257(4), 243(4), 200(3), 165 (60), 151 (72), 85 (100).
Anal. Calcd for C9H12S2Se4 (500.16): C 30.64; H 4.63; S 10.11; Se 63.28%. Found: C 30.81; H 4.33; S 10.03; Se 63.15%.
Methyl 3-{[(Z)-2-(vinylsulfanyl)ethenyl]selanylpropanoate (5a). A solution of NaBH4 (0.031 g, 0.82 mmol) and TEBAC (0.003 g) in water (0.5 mL) was added to a solution of diselenide 1 (0.082 g, 0.25 mmol) and methylacrylate (0.046 g, 0.53 mmol) in chloroform (1 mL) under argon for 30 min. The resulting mixture was stirred at room temperature for 1 h. Chloroform (5 mL) was added, and the mixture was stirred for 10 min. The organic layer was separated and dried over Na2SO4, and the solvent was removed under reduced pressure. The residue was subjected to column chromatography (silica gel 60, 70–230 mesh, eluent: hexane, then chloroform–hexane 1:3) to give the product (0.106 g, 85% yield).
1H NMR (400 MHz, CDCl3): δ 2.80 (t, 2H, CH2C(O), 3J 7.2 Hz), 2.97 (t, 2H, SeCH2, 3J 7.2 Hz), 3.71 (s, 3H, CH3), 5.26 (d, 1H, CH2=, 3Jtrans 16.9 Hz), 5.32 (d, 1H, CH2=, 3Jcis 9.8 Hz), 6.41 (dd, 1H, CH=CH2, 3Jtrans 16.8 Hz, 3Jcis 9.8 Hz), 6.62 (d, 1H, SCH=CHSe, 3J 8.3 Hz), 6.63 (d, 1H, SCH=CHSe, 3J 8.3 Hz).
13C NMR (100 MHz, CDCl3): δ 20.81 (SeCH2CH2, 1JSeC 60.9 Hz), 35.63 (SeCH2CH2), 51.75 (CH3), 113.50 (H2C=CHS), 121.92 (SCH=CHSe, 1JSeC 108.5 Hz), 124.51 (SCH=CHSe, 2JSeC 11.2 Hz), 129.88 (H2C=CHS), 172.24 (CH2C(O)).
77Se NMR (76 MHz, CDCl3): δ 271.56.
MS (EI), m/z (%): 252 (15) [M]+, 165 (48), 151 (2), 125 (31), 85 (100).
Anal. Calcd for C8H12O2SSe (251.21): C 38.25; H 4.81; S 12.76; Se 31.43%. Found: C 38.26; H 4.66; S 12.81; Se 31.31%.
Ethyl 3-{[(Z)-2-(vinylsulfanyl)ethenyl]selanylpropanoate (5b). Yield: 83%, a light-yellow oil. The product was purified by column chromatography (silica gel 60, 70–230 mesh, eluent: hexane, then chloroform–hexane 1:3).
1H NMR (400 MHz, CDCl3): δ 1.26 (t, 3H, CH3CH2, 3J 6.5 Hz), 2.70 (t, 2H, CH2C(O), 3J 8.1 Hz), 2.89 (t, 2H, SeCH2, 3J 8.1 Hz), 4.11 (q, 2H, CH2CH3, 2J 7.3 Hz), 5.18 (d, 1H, CH2=, 3Jtrans 17.0 Hz), 5.26 (d, 1H, CH2=, 3Jcis 10.0 Hz), 6.35 (dd, 1H, CH=CH2, 3Jtrans 17.0 Hz, 3Jcis 10.0 Hz), 6.53 (d, 1H, SCH=CHSe, 3J 8.1 Hz), 6.60 (d, 1H, SCH=CHSe, 3J 8.1 Hz).
13C NMR (100 MHz, CDCl3): δ 14.09 (CH3), 20.86 (SeCH2CH2, 1JSeC 59.9 Hz), 35.84 (SeCH2CH2), 60.63 (CH2CH3), 113.40 (H2C=CHS), 122.07 (SCH=CHSe, 1JSeC 108.2 Hz), 124.30 (SCH=CHSe, 2JSeC 12.0 Hz), 129.89 (H2C=CHS), 171.73 (CH2C(O)).
77Se NMR (76 MHz, CDCl3): δ 271.55.
MS (EI), m/z (%): 266 (35) [M]+, 165 (35), 151 (10), 125 (31), 85 (100).
Anal. Calcd for C9H14O2Sse (265.23): C 40.76; H 5.32; S 12.09; Se 29.77%. Found: C 40.49; H 5.29; S 12.19; Se 29.64%.
4-{[(Z)-2-(Vinylsulfanyl)ethenyl]selanyl}-2-butanol (5c). Yield: 87%, a light-yellow oil. The product was purified by column chromatography (silica gel 60, 70–230 mesh, eluent: hexane, then chloroform–hexane 1:2).
1H NMR (400 MHz, CDCl3): δ 1.24 (d, 3H, CH3, 2J 5.9 Hz), 1.55 (br. s, 1H, OH) 1.87 (m, 2H, CH2CH(OH)), 2.87 (m, 2H, SeCH2), 3.95 (m, 1H, CH(OH)CH3, 2J 6.3 Hz), 5.26 (d, 1H, CH2=, 3Jtrans 16.6 Hz), 5.32 (d, 1H, CH2=, 3Jcis 9.8 Hz), 6.42 (dd, 1H, CH=CH2, 3Jtrans 16.6 Hz, 3Jcis 9.8 Hz), 6.60 (d, 1H, SCH=CHSe, 3J 8.2 Hz), 6.65 (d, 1H, SCH=CHSe, 3J 8.2 Hz).
13C NMR (100 MHz, CDCl3): δ 23.40 (SeCH2CH2, 1JSeC 57.4 Hz), 23.50 (CH3), 39.73 (SeCH2CH2), 67.22 (CH(OH)CH3), 113.36 (H2C=CHS), 122.58 (SCH=CHSe, 1JSeC 108.7 Hz), 123.64 (SCH=CHSe, 2JSeC 11.4 Hz), 129.98 (H2C=CHS).
77Se NMR (76 MHz, CDCl3): δ 252.02.
MS (EI), m/z (%): 238 (35) [M]+, 165 (21), 151 (35), 133 (15), 85 (91), 45 (100).
Anal. Calcd for C8H14OSSe (237.22): C 40.50; H 5.95; S 13.52; Se 33.29. Found: C 40.49; H 5.76; S 13.59; Se 33.38%.
3-{[(Z)-2-(Vinylsulfanyl)ethenyl]selanyl}propanenitrile (6a). Yield: 36%, a light-yellow oil. The product was purified by column chromatography (silica gel 60, 70–230 mesh, eluent: hexane, then chloroform–hexane 1:3).
1H NMR (400 MHz, CDCl3): δ 2.80 (t, 2H, CH2CN, 3J 7.4 Hz), 2.95 (t, 2H, SeCH2, 3J 7.4 Hz), 5.30 (d, 1H, CH2=, 3Jtrans 16.8 Hz), 5.36 (d, 2H, CH2=, 3Jcis 10.0 Hz), 6.43 (dd 1H, CH=CH2, 3Jtrans 16.8 Hz, 3Jcis 10.0 Hz), 6.58 (d, 1H, SCH=CHSe, 3J 8.1 Hz), 6.76 (d, 1H, SCH=CHSe, 3J 8.1 Hz).
13C NMR (100 MHz, CDCl3): δ 19.77 (CH2CN, 2JSeC 6.8 Hz), 20.41 (SeCH2, 1JSeC 66.9 Hz), 114.24 (H2C=CHS), 118.40 (CN), 118.95 (SCH=CHSe, 1JSeC 107.0 Hz), 127.76 (SCH=CHSe, 2JSeC 11.0 Hz), 129.51 (H2C=CHS).
77Se NMR (76 MHz, CDCl3): δ 276.94.
MS (EI), m/z (%): 219 (20) [M]+, 165 (21), 137 (2), 107 (6), 85 (100), 58 (52).
Anal. Calcd for C7H9NSSe (218.18): C 38.53; H 4.16; N 6.42; S 14,70; Se 36.19%. Found: C 38.36; H 4.35; N 6.49; S 14,81; Se 36.34%.
3-{[(E)-2-(Vinylsulfanyl)ethenyl]selanyl}propanenitrile (6b). Yield: 23%, a light-yellow oil. The product was purified by column chromatography (silica gel 60, 70–230 mesh, eluent: hexane, then chloroform–hexane 1:3).
1H NMR (400 MHz, CDCl3): δ 2.79 (t, 2H, CH2CN, 3J 7.1 Hz), 2.91 (t, 2H, SeCH2, 3J 7.1 Hz), 5.35 (d, 1H, CH2=, 3Jtrans 16.7 Hz), 5.41 (d, 2H, CH2=, 3Jcis 9.7 Hz), 6.42 (dd 1H, CH=CH2, 3Jtrans 16.7 Hz, 3Jcis 9.7 Hz), 6.52 (d, 1H, SCH=CHSe, 3J 15.1 Hz), 6.65 (d, 1H, SCH=CHSe, 3J 15.1 Hz).
13C NMR (100 MHz, CDCl3): δ 19.31 (CH2CN, 2JSeC 6.3 Hz), 20.49 (SeCH2, 1JSeC 68.1 Hz), 114.57 (H2C=CHS), 115.72 (SCH=CHSe, 1JSeC 109.1 Hz), 118.38 (CN), 129.13 (SCH=CHSe, 2JSeC 11.2 Hz), 129.25 (H2C=CHS).
77Se NMR (76 MHz, CDCl3): δ 312.93.
MS (EI), m/z (%): 219 (16) [M]+, 165 (34), 137 (5), 107 (8), 85 (100), 58 (45).
Anal. Calcd for C7H9NSSe (218.18): C 38.53; H 4.16; N 6.42; S 14,70; Se 36.19%. Found: C 38.72; H 4.08; N 6.52; S 14,63; Se 36.38%.
(Z)-1-[(Chloromethyl)selanyl]ethenyl vinyl sulfide (7). A solution of NaBH4 (0.061 g, 1.6 mmol) and TEBAC (0.005 g) in water (0.5 mL) was added to a solution of diselenide 1 (0.174 g, 0.53 mmol) and methyl vinyl ketone (0.085 g (1.21 mmol) in methylene chloride (1 mL) under argon. The resulting mixture was stirred at room temperature for 3 h. Methylene chloride (5 mL) was added, and the mixture was stirred for 10 min. The organic layer was separated and dried over Na2SO4, and the solvent was removed under reduced pressure. The residue was subjected to column chromatography (silica gel 60, 70–230 mesh, eluent: hexane, then chloroform–hexane 1:3) to give butanol 6c (0.103 g, 41% yield) and products 7 (0.020 g, 9% yield) and 8 (0.043 g, 24% yield) as light-yellow oils.
1H NMR (400 MHz, CDCl3): δ 4.79 (s, 2H, CH2Cl), 5.29 (d, 1H, CH2=, 3Jtrans 16.6 Hz), 5.36 (d, 1H, CH2=, 3Jcis 9.8 Hz), 6.42 (dd, 1H, CH=CH2, 3Jtrans 16.6 Hz, 3Jcis 9.8 Hz), 6.76 (d, 1H, SCH=CHSe, 3J 8.1 Hz), 6.81 (d, 1H, SCH=CHSe, 3J 8.1 Hz).
13C NMR (100 MHz, CDCl3): δ 37.51 (CH2Cl, 1JSe-C 94.0 Hz), 114.20 (H2C=CHS), 120.68 (CH=CHSe, 1JSe-C 103.5 Hz), 126.33 (SCH=CHSe, 2JSe-C 11.9 Hz), 129.47 (H2C=CHS).
77Se NMR (76 MHz, CDCl3): δ 396.12.
MS (EI), m/z (%): 214 (23) [M]+, 165 (28), 85 (100) 58 (50), 45 (48).
Anal. Calcd for C5H7ClSSe (213.59): C 28.12; H 3.30; Cl 16.60; S 15.01; Se 36.97%. Found: C 28.34; H 3.36; Cl 16.36; S 15.12; Se 37.13%.
Bis[(Z)-2-(vinylsulfanyl)ethenylselanyl]methane (8). Yield: 24%, a light-yellow oil. The product was purified by column chromatography (silica gel 60, 70–230 mesh, eluent: hexane, then chloroform–hexane 1:3).
1H NMR (400 MHz, CDCl3): δ 3.95 (s, 2H, SeCH2Se, 2JSe-H 15.5 Hz), 5.29 (d, 2H, CH2=, 3Jtrans 16.5 Hz), 5.35 (d, 2H, CH2=, 3Jcis 9.7 Hz), 6.43 (dd, 2H, CH=CH2, 3Jtrans 16.5 Hz, 3Jcis 9.7 Hz, 2JSe-H 41.2 Hz), 6.70 (d, 2H, SCH=CHSe, 3J 8.0 Hz), 6.76 (d, 2H, SCH=CHSe, 3J 8.0 Hz).
13C NMR (100 MHz, CDCl3): δ 17.68 (SeCH2Se, 1JSe-C 83.4 Hz), 113.89 (H2C=CHS), 122.45 (CH=CHSe, 1JSe-C 106.6 Hz), 125.23 (SCH=CHSe, 2JSe-C 11.9 Hz), 129.76 (H2C=CHS).
77Se NMR (76 MHz, CDCl3): 300.29.
MS (EI), m/z (%): 344 (12) [M]+, 165 (28), 85 (100) 58 (50), 45 (48).
Anal. Calcd for C9H12S2Se2 (342.24): C 31.58; H 3.53; S 18.74; Se 46.14%. Found: C 31.87; H 3.62; S 18.83; Se 46.16%.

4. Conclusions

Divinyl sulfide and its derivatives are highly reactive cross-linking agents and monomers for the preparation of various valuable polymeric materials, as well as starting compounds for the synthesis of functionalized organosulfur products and heterocycles [42,43]. A number of 1,3-thiaselenole derivatives are promising electron donor compounds for the preparation of conducting materials (Figure 1) [38,39,40,41].
The efficient regioselective synthesis of new families of organylselanyl-functionalized 1,3-thiaselenoles 3a–e, 4 and divinyl sulfides 5a–c, 6a, b, 7 and 8 in high yields under phase transfer catalysis conditions was developed based on the generation of sodium [(Z)-2-(vinylsulfanyl)ethenyl]selenolate and 1,3-thiaselenol-2-ylmethylselenolate. The nucleophilic addition of the sodium selenolates to the activated alkenes acrylonitrile, acrylamide, methyl vinyl ketone, methyl, and ethyl acrylates proceed in a regioselective fashion exclusively at the terminal carbon atom of the double bond.
Unexpected but promising products, functionalized 1,3-thiaselenols 3a–e, 4, and divinyl sulfides 5c, 7, and 8, were obtained as a result of unusual reactions accompanied by nucleophilic substitution of the chlorine atom in methylene chloride and hydrogenation.
A single-stage method for the synthesis of 3-hydroxybutyl selenides from methyl vinyl ketone, organic diselenides, and sodium borohydride under phase transfer catalysis conditions was proposed.
The synthesized products are new promising starting materials for the preparation of polyfunctional organochalcogen compounds with possible biological activity.

Supplementary Materials

The following supporting information can be downloaded at: https://www.mdpi.com/article/10.3390/catal13081227/s1: 1H, 13C and 77Se NMR spectra of the obtained compounds.

Author Contributions

Methodology, S.V.A. and A.S.F.; investigation, A.S.F., N.A.M. and A.I.A.; data curation, A.S.F., S.V.A., N.A.M. and A.I.A.; writing—original draft preparation, V.A.P. and A.S.F.; writing—review and editing, V.A.P. All authors have read and agreed to the published version of the manuscript.

Funding

This research received no external funding.

Data Availability Statement

Not applicable.

Acknowledgments

The authors thank Baikal Analytical Center SB RAS for providing the instrumental equipment.

Conflicts of Interest

The authors declare no conflict of interest.

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Catalysts 13 01227 g001
Figure 1. Examples of practical usage of 1,3-thiaselenole and vinyl sulfide derivatives.
Figure 1. Examples of practical usage of 1,3-thiaselenole and vinyl sulfide derivatives.
Catalysts 13 01227 g001
Catalysts 13 01227 sch001
Scheme 1. The efficient synthesis of compounds 1 and 2 from 2-bromomethyl-1,3-thiaselenole.
Scheme 1. The efficient synthesis of compounds 1 and 2 from 2-bromomethyl-1,3-thiaselenole.
Catalysts 13 01227 sch001
Catalysts 13 01227 sch002
Scheme 2. The generation of sodium [(Z)-2-(vinylsulfanyl)ethenyl]selenolate and 1,3-thiaselenol-2-ylmethylselenolate from compounds 1 and 2.
Scheme 2. The generation of sodium [(Z)-2-(vinylsulfanyl)ethenyl]selenolate and 1,3-thiaselenol-2-ylmethylselenolate from compounds 1 and 2.
Catalysts 13 01227 sch002
Catalysts 13 01227 sch003
Scheme 3. The efficient synthesis of compounds 3a–e from selenocyanate 2 and activated alkenes (the 77Se NMR data are included).
Scheme 3. The efficient synthesis of compounds 3a–e from selenocyanate 2 and activated alkenes (the 77Se NMR data are included).
Catalysts 13 01227 sch003
Catalysts 13 01227 sch004
Scheme 4. The reaction of compound 2 with methyl vinyl ketone in methylene chloride (the 77Se NMR data are included).
Scheme 4. The reaction of compound 2 with methyl vinyl ketone in methylene chloride (the 77Se NMR data are included).
Catalysts 13 01227 sch004
Catalysts 13 01227 sch005
Scheme 5. The efficient synthesis of compounds 5a–c from diselenide 1 and activated alkenes (the 77Se NMR data are included).
Scheme 5. The efficient synthesis of compounds 5a–c from diselenide 1 and activated alkenes (the 77Se NMR data are included).
Catalysts 13 01227 sch005
Catalysts 13 01227 sch006
Scheme 6. The reaction of compound 1 with acrylonitrile (the 77Se NMR data are included).
Scheme 6. The reaction of compound 1 with acrylonitrile (the 77Se NMR data are included).
Catalysts 13 01227 sch006
Catalysts 13 01227 sch007
Scheme 7. The reaction of compound 1 with methyl vinyl ketone in methylene chloride (the 77Se NMR data are included).
Scheme 7. The reaction of compound 1 with methyl vinyl ketone in methylene chloride (the 77Se NMR data are included).
Catalysts 13 01227 sch007
Catalysts 13 01227 sch008
Scheme 8. The reaction of diphenyl diselenide with methyl vinyl ketone and sodium borohydride under phase transfer catalysis conditions.
Scheme 8. The reaction of diphenyl diselenide with methyl vinyl ketone and sodium borohydride under phase transfer catalysis conditions.
Catalysts 13 01227 sch008
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MDPI and ACS Style

Filippov, A.S.; Amosova, S.V.; Makhaeva, N.A.; Albanov, A.I.; Potapov, V.A. Efficient Regioselective Synthesis of Novel Ensembles of Organylselanyl-Functionalized Divinyl Sulfides and 1,3-Thiaselenoles under Phase Transfer Catalysis Conditions. Catalysts 2023, 13, 1227. https://doi.org/10.3390/catal13081227

AMA Style

Filippov AS, Amosova SV, Makhaeva NA, Albanov AI, Potapov VA. Efficient Regioselective Synthesis of Novel Ensembles of Organylselanyl-Functionalized Divinyl Sulfides and 1,3-Thiaselenoles under Phase Transfer Catalysis Conditions. Catalysts. 2023; 13(8):1227. https://doi.org/10.3390/catal13081227

Chicago/Turabian Style

Filippov, Andrey S., Svetlana V. Amosova, Nataliya A. Makhaeva, Alexander I. Albanov, and Vladimir A. Potapov. 2023. "Efficient Regioselective Synthesis of Novel Ensembles of Organylselanyl-Functionalized Divinyl Sulfides and 1,3-Thiaselenoles under Phase Transfer Catalysis Conditions" Catalysts 13, no. 8: 1227. https://doi.org/10.3390/catal13081227

APA Style

Filippov, A. S., Amosova, S. V., Makhaeva, N. A., Albanov, A. I., & Potapov, V. A. (2023). Efficient Regioselective Synthesis of Novel Ensembles of Organylselanyl-Functionalized Divinyl Sulfides and 1,3-Thiaselenoles under Phase Transfer Catalysis Conditions. Catalysts, 13(8), 1227. https://doi.org/10.3390/catal13081227

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