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Article

Regio- and Stereoselective One-Pot Synthesis of New Heterocyclic Compounds with Two Selenium Atoms Based on 2-Bromomethyl-1,3-thiaselenole Using Phase Transfer Catalysis

by
Svetlana V. Amosova
,
Andrey S. Filippov
,
Vladimir A. Potapov
* and
Alexander I. Albanov
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 2022, 12(10), 1236; https://doi.org/10.3390/catal12101236
Submission received: 31 August 2022 / Revised: 9 October 2022 / Accepted: 13 October 2022 / Published: 14 October 2022
(This article belongs to the Special Issue The Influence of Phase Transfer Catalysis (PTC) in the Synthesis of Bioactive Compounds)
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Abstract

:
To date, not a single representative of 2,3-dihydro-1,4-thiaselenin-2-yl selenides has been described in the literature. The reaction of 2-bromomethyl-1,3-thiaselenole with potassium selenocyanate at low temperature was accompanied by a rearrangement with ring expansion leading to six-membered 2,3-dihydro-1,4-thiaselenin-2-yl selenocyanate, which was used for the generation of sodium dihydro-1,4-thiaselenin-2-yl selenolate. The latter intermediate was involved in situ in the nucleophilic substitution and addition reactions under phase transfer catalysis conditions. The nucleophilic substitution reactions with alkyl halides gave alkyl, allyl and propargyl 2,3-dihydro-1,4-thiaselenin-2-yl selenides in 93–98% yields. The addition reactions of dihydro-1,4-thiaselenin-2-yl selenolate anion to alkyl acrylates, acrylonitrile and alkyl propiolates proceeded in a regio- and stereoselective fashion affording corresponding functionalized 2,3-dihydro-1,4-thiaselenin-2-yl selenides in 93–98% yields. Thus, the regio- and stereoselective one-pot synthesis of a novel family of 2,3-dihydro-1,4-thiaselenin-2-yl selenides has been developed based 2-bromomethyl-1,3-thiaselenole, potassium selenocyanate, alkyl halides and compound with activated double and triple bonds.

1. Introduction

The development of synthetic approaches to novel classes of organoselenium compounds continues to be a very active area of research driven by their promising biological properties. In fact, a diverse variety of organoselenium compounds and especially selenium-containing heterocycles are well-known for their antitumor, antibacterial, antiviral, antifungal, anti-inflammatory, anti-HIV, antioxidant and glutathione peroxidase-like activities [1,2,3,4,5,6,7,8,9,10,11,12,13,14,15,16,17,18,19].
Perhaps the most famous selenium-containing heterocyclic compound is ebselen, a novel anti-inflammatory drug, which also exhibit neuroprotective and glutathione peroxidase-like properties [6,7,8]. These valuable properties combined with low toxicity of ebselen have led to therapeutic application of this compound, which has undergone evaluation in clinical trials. This compound has been also used for the treatment and prevention of cardiovascular diseases and ischemic stroke [6,7,8]. It has been recently shown that ebselen inhibits CoV2 activity and viral replication [7].
The application of organoselenium compounds as electron donors for the preparation of organic metals, superconductors, semiconductors, ferromagnets and organic Dirac materials is another area of current interest [20,21,22,23,24,25,26,27,28,29]. Examples of six-membered selenium heterocycles of practical importance 1–7 are shown in Figure 1 [13,14,15,16,17,18,19].
The synthetic organoselenium chemistry has been changed over the last two decades resulting in the development of easily accessible and efficient reagents, thus enabling the easy access to various classes of novel organoselenium compounds [30,31,32,33,34,35,36,37,38,39,40,41,42,43,44,45,46,47,48,49,50,51,52,53,54]. Novel electrophilic reagents, selenium dihalides, have been involved in the synthesis of organoselenium compounds. The application of selenium dihalides has opened up new possibilities for the development of synthetic approaches to novel classes of organoselenium compounds. Efficient approaches to selenium-containing heterocycles based on cyclization, annulation, annulation–functionalization, and selenocyclofunctionalization reactions have been developed [30,31,32,33,34,35,36,37,38,39,40,41,42,43,44,45,46].
2-Bromomethyl-1,3-thiaselenole (8) is a new unsaturated sulfur/selenium-containing heterocycle, a unique reagent with unexpected behavior in nucleophilic substitution reactions due to high anchimeric assistance effect of the selenium atom [54]. Thiaselenole 8 was obtained based on the reaction of selenium dibromide with divinyl sulfide [50].
We assume that thiaselenole 8 occurs in equilibrium with corresponding seleniranium cation, which considerably determines its chemical behavior in nucleophilic substitution reactions. Efficient regio- and stereoselective approaches to novel heterocyclic organochalcogen compounds by reactions of thiaselenole 8 with a variety of nucleophilic reagents have been developed [47,48,49,50,51,52,53].
The reaction of thiaselenole 8 with ammonium thiocyanate (acetonitrile, room temperature, 3 h) was accompanied by a rearrangement with ring expansion affording 2,3-dihydro-1,4-thiaselenin-2-yl thiocyanate (9) in 95% yield (Scheme 1) [55]. However, when the reaction was carried out at 60 °C for 25 h, five-membered 1,3-thiaselenol-2-ylmethyl thiocyanate (10) was obtained in 40% yield as a result of rearrangement of six-membered thiocyanate 9 [55]. The compound 10 was believed to be a more stable thermodynamic product, while six-membered thiocyanate 9 was considered a kinetic product.
The reaction of thiaselenole 8 with potassium selenocyanate in acetonitrile at room temperature for five minutes afforded 1,3-thiaselenol-2-ylmethyl selenocyanate (11) in 97% yield (Scheme 1) [56].

2. Results and Discussion

The aim of this research is the development of a regio- and stereoselective one-pot synthesis of a novel family of 2,3-dihydro-1,4-thiaselenin-2-yl selenides, containing various functions including carboxyl and vinyl groups. In fact, dihydro-1,4-thiaselenines are a very rare class of compounds. Only two representatives of dihydro-1,4-thiaselenines have been described in the literature prior to our research [57]. It is worth noting that a dihydro-1,4-thiaselenine derivative (2-(4-chlorophenyl)-6-phenyl-2,3-dihydro-1H-1,4- thiaselenine-1,1-dione, Figure 1) exhibits antibacterial and antifungal activities [19]. To date, not a single representative of 2,3-dihydro-1,4-thiaselenin-2-yl selenides has been described in the literature.
We assumed that the reaction of thiaselenole 8 with potassium selenocyanate initially led to the kinetic product, an intermediate six-membered selenocyanate, similarly to the reaction of thiaselenole 8 with ammonium thiocyanate (Scheme 1). Indeed, when the reaction thiaselenole 8 with potassium selenocyanate was monitored by NMR at low temperature (0 °C), the formation of intermediate 2,3-dihydro-1,4-thiaselenin-2-yl selenocyanate (12) was observed followed by its rearrangement to five-membered selenocyanate (11) (Scheme 2).
Thus, like the formation of 1,3-thiaselenol-2-ylmethyl thiocyanate 10 by rearrangement of 2,3-dihydro-1,4-thiaselenin-2-yl thiocyanate 9 (Scheme 1), the reaction of thiaselenole 8 with potassium selenocyanate initially led to the six-membered thiaselenine 12 (the kinetic product), which underwent a rearrangement to a five-membered selenocyanate 11 (the thermodynamic product). These rearrangements occur by nucleophilic attack of the selenocyanate anion at two different carbon atoms of the seleniranium intermediate A (Scheme 2).
The reaction of thiaselenole 8 with potassium selenocyanate proceeded smoothly in acetonitrile at low temperature (0 °C) affording selenocyanate 12. Reduction of organic selenocyanates to corresponding sodium organylselenolate by the action of sodium borohydride can be carried out in alcohol or in aqueous solutions since sodium borohydride is soluble in these media but exhibits negligible solubility in most common organic solvents. However, the use of alcohols (methanol, ethanol) as solvents for this reaction led to the formation of by-products as a result of nucleophilic substitution of bromine by methoxy or ethoxy groups. Previously we reported that the bromine atom in thiaselenole 8 can be easily substituted by the alkoxy group [58].
We succeeded in trapping intermediate dihydro-1,4-thiaselenin-2-yl selenocyanate 12 at low temperature (0 °C) and its conversion to sodium dihydro-1,4-thiaselenin-2-yl selenolate 13 by the action of sodium borohydride in an aqueous solution (Scheme 2). The intermediate selenolate 13 was involved in nucleophilic substitution reactions as well as in addition reactions to double and triple bonds affording corresponding dihydro-1,4-thiaselenin-2-yl selenides in high yields.
The intermediate sodium dihydro-1,4-thiaselenin-2-ylselenolate 13 was able to oxidize by air. However, we found that this undesirable transformation can be prevented by carrying out the reaction under an argon atmosphere and using an excess of sodium borohydride compared to stoichiometric amounts.
The relative efficiency of a number of catalysts: tetrabutylammonium chloride (TBAC), tetrabutylammonium bromide (TBAB), triethylbenzylammonium chloride (TEBAC), triethylbenzylammonium bromide (TEBAB) and Aliquat 336 TG was evaluated in the reaction of sodium dihydro-1,4-thiaselenin-2-ylselenolate 13 with propyl bromide under the same conditions (equimolar amounts of potassium selenocyanate and thiaselenole 8 (1.5 mmol), propyl bromide (1.7 mmol), the catalyst (3% mol), sodium borohydride/water/chloroform, 4 h, room temperature, under an argon atmosphere).
Based on the obtained product yields, it was concluded that TBAB showed the best result (the 98% yield of the product 14, Scheme 3). The product 14 was obtained in 88–90% yield using TBAC and Aliquat 336 TG as catalysts. TEBAC and TEBAB were found to be less effective (74% and 70% yields of the product 14, Scheme 3). Only 5% yield of the product 14 was obtained in the control experiment without the phase transfer catalyst under the same conditions.
Since TBAB proved to be the best catalyst for the reaction of sodium dihydro-1,4-thiaselenin-2-ylselenolate 6, subsequent experiments were carried out using TBAB. Along with propyl bromide, alkyl halides such as methyl iodide and ethyl bromides were involved in the reaction under the same conditions affording methyl and ethyl 2,3-dihydro-1,4-thiaselenin-2-yl selenides 15 and 16 in 93% and 96% yields, respectively (Table 1).
The reaction was carried out as a one-pot procedure. Potassium selenocyanate was added to a cooled to 0 °C (an ice bath) solution of thiaselenole 8 in acetonitrile and the mixture was stirred for 1 h at ~0 °C followed by solvent removing under reduced pressure at ~0 °C to give selenocyanate 12 as a residue. A cooled to ~0 °C solution of alkyl halides in chloroform and TBAB as a catalyst (3% mol) were added to the residue followed by the dropwise addition of a cooled to ~0 °C aqueous solution of sodium borohydride in degassed water under an argon atmosphere. The mixture was stirred for 2.5 h at ~0 °C on the ice bath, then the ice bath was removed and the mixture was stirred for 30 min while warming to room temperature. The products 14–16 were obtained in 93–98% yields after extraction with methylene chloride followed by removing the solvent under reduced pressure. This methodology allowed obtaining the target products in high yields and with good purity.
In the case of highly reactive methyl iodide, the slightly reduced yield of the product 15 (93%) was attributed to the possibility of alkylation at the selenium atoms of compound 15 to form water-soluble selenonium salts of the R3Se−Hal+ type, which remain in the aqueous phase.
The intermediate sodium dihydro-1,4-thiaselenin-2-ylselenolate 13, as well as sodium borohydride, are soluble in water, but not in organic phase. We suppose that TBAB can catalyze not only the nucleophilic reaction of the intermediate sodium selenate 13, but also the reduction of selenocyanate 12 with sodium borohydride.
Unsaturated halogen-containing reagents, allyl and propargyl bromides, were involved in the nucleophilic substitution reaction with sodium dihydro-1,4-thiaselenin-2-yl selenolate 13 generated in situ from selenocyanate 12 (Table 1). The reactions with allyl and propargyl bromides proceeded faster than with alkyl bromides. It was found that stirring the mixture for 90 min at ~0 °C and for 30 min after removing on the ice bath is sufficient to obtain allyl and propargyl selenides 17 and 18 in near quantitative yields (97–98%) (total duration of the experiment was 3 h, Table 1).
The nucleophilic addition of sodium thiaselenin-2-yl selenolate 13 to the activated double bond of alkyl acrylates and acrylonitrile was found to proceed slower compared to the nucleophilic substitution reaction with alkyl halides (Table 1). However, we found that doubling the amount of catalyst (from 3% mol to 6% mol) and increasing the duration of the reaction makes it possible to effectively carried out the nucleophilic addition reaction and to obtain 3-(1,2-dihydro-1,4-thiaselenin-2-ylselanyl)propanenitrile 19 and alkyl 3-(2,3-dihydro-1,4-thiaselenin-2-ylselanyl)-2-propanoates 20 and 21 in 93–96% yields (Table 1). It should be emphasized that the reactions with alkyl acrylates and acrylonitrile proceeded with high regioselectivity.
The regio- and stereoselective synthesis of alkyl (Z)-3-(2,3-dihydro-1,4-thiaselenin-2-ylselanyl)acrylates 22 and 23 in 97–98% yields was developed based on nucleophilic addition of selenolate 13 to alkyl propiolates (Table 1).
Selenium-centered anions are strong nucleophiles, which are superior to analogous sulfur-centered anions in nucleophilicity. It is known that reactions of selenium-centered nucleophiles with acetylenes often occurs stereoselectively as anti-addition to the triple bond giving vinyl selenides with (Z)-configuration [59,60]. The nucleophilic addition of sodium selenolate 13 to alkyl propiolates occurs in a regio- and stereoselective fashion affording products with (Z)-stereochemistry. The carbonyl group stabilizes the negative charge on the adjacent carbon atom in the intermediate derived from addition of sodium selenolate 13 to the activated triple bond of alkyl propiolates and determines the regioselectivity of the reaction.
The results obtained are summarized in Table 1. The reactions with allyl and propargyl bromides took less time and proceeded faster than with alkyl bromides (Table 1, runs 1–5). The addition reactions to acrylonitrile and alkyl acrylates required increasing the duration of the reaction and the content of the catalyst in comparison with the alkylation reactions in order to effectively carry out the process (Table 1, runs 1–8). The nucleophilic addition of sodium selenolate 13 to the activated triple bond of alkyl propiolates proceeded faster than to the activated double bond of alkyl acrylates (Table 1, runs 7–10). The reaction with alkyl propiolates took less time (4 h instead of 5 h) to obtain the products 22 and 23 in near quantitative yields.
The structural assignment of the synthesized compounds was made based on 1H-, 13C-, and 77Se [61] NMR spectroscopy and mass spectrometry. The composition of the compounds was confirmed by elemental analysis. The obtained (2,3-dihydro-1,4-thiaselenin-2-yl) selenides 14–23 and the 77Se-NMR data (ppm) are shown in Scheme 4.
The selenium atom in the 2,3-dihydro-1,4-thiaselenine cycle of selenides 14–23 resonates in the region of 220.5–236.3 ppm. The same region was observed by us earlier in the 77Se-NMR spectra of other 2,3-dihydro-1,4-thiaselenine derivatives including 2-(organylsulfanyl)-2,3-dihydro-1,4-thiaselenines [48,52]. It is worthy to note that the selenium atom in isomeric five-membered 2-substituted methyl-1,3-thiaselenole derivatives including compound 8 resonates in the downfield region of 513–528 ppm [51].
The signals of the selenium atom in the side chain are observed in a wider range of chemical shifts (359.8–548 ppm, Scheme 4), which depend on the nature of the adjacent functional group. The unshared electron pair of the selenium atom in the side chain is in conjugation with a double bond as well as with an electron-withdrawing carbonyl group in vinylic selenides 22 and 23, and highest downfield shift of the selenium signals (546.6–548 ppm) are observed for compounds 22 and 23.
In the 1H-NMR spectra of vinyl selenides 22 and 23, two doublets of olefinic protons of the SeCH=CHCOOAlk group are observed with a spin-spin coupling constant 3JH,H = 9.5 Hz, the value of which indicates (Z)-configuration of these compounds.
Molecular ions were detected in the mass spectra of synthesized 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-NMR).
Mass spectra were recorded on a Shimadzu GCMS-QP5050A (Shimadzu Corporation, Kyoto, Japan) with electron impact (EI) ionization (70 eV). Elemental analysis was performed on a Thermo Scientific Flash 2000 Elemental Analyzer (Thermo Fisher Scientific Inc., Milan, Italy). The distilled organic solvents and degassed water were used in syntheses.

3.2. Modified Procedure for the Preparation of Starting 2-Bromomethyl-1,3-thiaselenole

2-Bromomethyl-1,3-thiaselenole (8). A solution of bromine (1.6 g, 10 mmol) in carbon tetrachloride (5 mL) was added dropwise to a mixture of powdered selenium (0.79 g, 10 mmol) in carbon tetrachloride (5 mL) and the mixture was stirred until the solid dissolved. The obtained solution of selenium dibromide in carbon tetrachloride and a solution of divinyl sulfide (0.86 g, 10 mmol) in carbon tetrachloride (10 mL) were simultaneously added dropwise over 1 h to a flask containing carbon tetrachloride (10 mL) so that the molar ratio of both reagents in the mixture was approximately 1:1. The reaction mixture was stirred for 4 h and a solution of pyridine (0.95 g, 12 mmol) in carbon tetrachloride (10 mL) was added over 15 min, and the mixture was stirred overnight. The reaction mixture was filtered, and most of the solvent was removed by rotary evaporation. The residue (approximately 10 mL) was filtered and the solvent and the remaining pyridine were removed from the filtrate in vacuo to give pure thiaselenole 8 (1.95 g, 80% yield) as a brown oil.

3.3. Synthesis of Selenocyanates 11 and 12

1,3-Thiaselenol-2-ylmethyl selenocyanate (11). Powdered selenium (158 mg, 2 mmol) was added to a solution of KCN (130 mg, 2 mmol) in MeOH (10 mL). The mixture was stirred at room temperature until the solid disappeared (usually ~0.5 h). The solvent was removed by rotary evaporator and a solution of thiaselenole 8 (488 mg, 2.00 mmol) in MeCN (10 mL) was added to the residue and the mixture was stirred at room temperature for 1 h and filtered. The solvent was removed in vacuum giving product 11 as a light yellow oil. Yield: 533 mg (99%). 1H NMR (400 MHz, CDCl3), δ (ppm): 6.67 (d, 3JH,H = 6.3 Hz, 2JSe,H = 48.5 Hz, 1H, SeCH=CHS), 6.43 (d, 3JH,H = 6.3 Hz, 2H, SCHSe), 5.08 (dd, 3JH,H = 7.1 Hz, 3JH,H = 8.2Hz, 2JSe,H = 20.0 Hz, 1H, SCHSe), 3.48 (dd, 3JH,H = 7.1 Hz, 2JH,H = 12.2 Hz, 1H, CHbSeCN), 3.41 (dd, 2JH,H = 12.2 Hz, 3JH,H = 8.2 Hz, 1H, CHaSeCN).
13C NMR (100 MHz, CDCl3), δ (ppm): 119.26 (SeCH=CHS), 113.75 (1JSe,C = 106 Hz, SeCH=CHS), 101.07 (SeCN), 46.48 (1JSe,C = 70 Hz, SCHSe), 37.97 (1JSe,C = 52 Hz, CH2SeCN).
77Se NMR (76.3 MHz, CDCl3), δ (ppm): 539.6 (SCHSe), 228.4 (CH2SeCN).
MS (EI): m/z (%) = 271 (50, M+), 165 (39), 151 (100), 107 (23), 85 (93), 84 (86), 71 (64), 59 (66), 58 (87), 45 (71).
Anal. Calcd for C5H5NSSe2: C 22.32; H 1.87; N 5.21; S 11.92: Se, 58.69. Found: C 21.98; H 1.69; N 4.94; S 12.27: Se, 59.01.
2,3-Dihydro-1,4-thiaselenin-2-yl selenocyanate (12). A cooled to 0 °C solution of potassium selenocyanate (72 mg, 0.50 mmol) in MeCN (0.25 mL) was added to a cooled to 0 °C solution of thiaselenole 8 (122 mg, 0.50 mmol) in MeCN (0.25 mL) with stirring. The mixture was stirred on the ice bath at ~0 °C for 0.5 h under an argon atmosphere and the solvent was removed in vacuum giving a light yellow oil, which was analyzed by 1H- and 13C-NMR. The mixture contained selenocyanate 12 and thiaselenole 8. The following spectral characteristics of selenocyanate 12 were detected. 1H NMR (400 MHz, CDCl3), δ (ppm): 6.53 (dd, 3JH,H = 9.9 Hz, 1H, SeCH=CHS), 6.37 (d, 3JH,H = 9.9 Hz, 1H, SeCH=CHS), 5.21 (dd, 3JH,H = 2.1 Hz, 3JH,H = 6.6 Hz, 1H, SCHSe), 3.79 (dd, 2JH,H = 12.4 Hz, 3JH,H = 2.1 Hz, 1H, =CHSeCHa), 3.33 (dd, 2JH,H = 12.4 Hz, 3JH,H = 6.6 Hz, 1H, =CHSeCHb).
13C NMR (100 MHz, CDCl3), δ (ppm): 116.76 (SeCH=CHS), 110.66 (SeCH=CHS), 101.88 (SeCN), 43.07 (SCHSe), 26.07 (=CHSeCH2).

3.4. Synthesis of 2,3-Dihydro-1,4-thiaselenin-2-yl Alkyl Selenides

General procedure for the synthesis of compounds 14–16. Potassium selenocyanate (216 mg, 1.5 mmol) was added to a cooled to 0 °C (an ice bath) solution of thiaselenole 8 (366 mg, 1.5 mmol) in MeCN (1 mL) with stirring. The mixture was stirred at ~0 °C for 1 h and the solvent was removed under reduced pressure at ~0 °C. A cooled to ~0 °C solution of alkyl halides (1.7 mmol) in chloroform (1 mL) and tetrabutylammonium bromide (15 mg, 3% mol) were added to the residue followed by the dropwise addition of a cooled to ~0 °C (an ice bath) solution of NaBH4 (0.086 g, 2.26 mmol) in degassed water (0.8 mL) under an argon atmosphere. The mixture was stirred for 2.5 h at ~0 °C on the ice bath, then the ice bath was removed and the mixture was stirred for 30 min while warming to room temperature. Degassed water (3 mL) was added and the reaction mixture was extracted with methylene chloride (3 × 8 mL). The organic phase was dried over Na2SO4 and the solvent was removed by a rotary evaporator. The residue was dried in vacuum giving products 14–16 in 93–98% yields.
2,3-Dihydro-1,4-thiaselenin-2-yl propyl selenide (14). Yield: 420 mg (98%), a light-yellow oil. 1H-NMR (400 MHz, CDCl3): δ: 1.03 (3H, t, 3J = 7.4 Hz, CH3), 1.74–1.82 (2H, m, CH3CH2), 2.78–2.86 (2H, m, SeCH2CH2CH3), 3.34 (1H, dd, 2J = 11.7 Hz, 3J = 10.3 Hz, CH2Se in cycle), 3.49 (1H, dd, 2J = 11.7 Hz, 3J = 2.8 Hz, CH2Se in cycle), 4.50 (1H, dd, 3J = 10.3 Hz, 3J = 2.8 Hz, SCHSe), 6.42 (1H, d, 3J = 9.7 Hz, =CHS), 6.51 (1H, d, 3J = 9.7 Hz, =CHSe).
13C-NMR (100 MHz, CDCl3): 14.39 (CH3), 23.84 (CH2CH3), 25.54 (1JSeC = 62.1 Hz, SeCH2 in cycle), 26.88 (1JSeC = 62.6 Hz, SeCH2CH2CH3), 34.82 (1JSeC = 78.1 Hz, SCHSe), 108.74 (1JSeC = 115.8 Hz, =CHSe), 120.66 (=CHS).
77Se NMR (100 MHz, CDCl3): δ 237.2 (cycle), 359.8.
MS: m/z (%): 288 (11) [M]+, 165 (54), 151 (26), 85 (100).
Anal. Calcd for C7H12SSe2: C 29.38; H 4.23; S 11.21; Se 55.19%. Found: C 29.54; H 4.18; S 11.10; Se 54.83%.
2,3-Dihydro-1,4-thiaselenin-2-yl methyl selenide (15). Yield: 360 mg (93%), a light-yellow oil. 1H-NMR (400 MHz, CDCl3): δ: 2.17 (3H, s, CH3), 3.28 (1H, dd, 2J = 12.0 Hz, 3J = 10.3 Hz, CH2Se), 3.47 (1H, dd, 2J = 12.0 Hz, 3J = 2.6 Hz, CH2Se), 4.46 (1H, dd, 3J = 10.3 Hz, 3J = 2.6 Hz, SCHSe), 6.40 (1H, d, 3J = 9.9 Hz, =CHS), 6.48 (1H, d, 3J = 9.9 Hz, =CHSe).
13C-NMR (100 MHz, CDCl3): δ 3.68 (1JSeC = 64.6 Hz, SeCH3), 25.02 (1JSeC = 60.6 Hz, SeCH2), 35.10 (1JSeC = 76.6 Hz, SCHSe), 108.69 (1JSeC = 115.5 Hz, =CHSe), 120.64 (=CHS).
77Se NMR (100 MHz, CDCl3): δ 232.5 (cycle), 283.2.
MS: m/z (%): 260 (29) [M]+, 165 (3), 151 (100), 107 (9), 107(12), 85 (45).
Anal. Calcd for C5H8SSe2: C 23.27; H 3.12; S 12.42; Se 61.18%. Found: C 22.92; H 3.18; S 12.67; Se 60.89%.
2,3-Dihydro-1,4-thiaselenin-2-yl ethyl selenide (16). Yield: 392 mg (96%), a light-yellow oil. 1H-NMR (400 MHz, CDCl3): δ: 1.50 (3H, t, 3J = 7.4 Hz, CH3CH2), 2.83 (2H, m, SeCH2CH3), 3.32 (1H, dd, 2J = 11.6 Hz, 3J = 10.2 Hz, CH2Se in cycle), 3.44 (1H, dd, 2J = 11.6 Hz, 3J = 2.8 Hz, CH2Se in cycle), 4.45 (1H, dd, 3J = 10.2 Hz, 3J = 2.8 Hz, SCHSe), 6.36 (1H, d, 3J = 9.8 Hz, =CHS), 6.42 (1H, d, 3J = 9.8 Hz, =CHSe).
13C-NMR (100 MHz, CDCl3): 15.87 (CH3), 18.33 (1JSeC = 61.5 Hz, SeCH2CH3), 25.58 (1JSeC = 62.2 Hz, SeCH2 in cycle), 34.70 (1JSeC = 78.2 Hz, SCHSe), 108.84 (1JSeC = 115.7 Hz, =CHSe), 120.64 (=CHS).
77Se NMR (100 MHz, CDCl3): δ 236.3 (cycle), 393.2.
MS: m/z (%): 272 (41) [M]+, 165 (100), 151 (38), 108 (21), 85 (97).
Anal. Calcd for C6H10SSe2: C 26.48; H 3.70; S 11.78; Se 58.03%. Found: C 26.92; H 3.55; S 12.01; Se 57.70%.

3.5. Synthesis of 2,3-Dihydro-1,4-thiaselenin-2-yl Allyl and 2-Propynyl Selenides 17 and 18

General procedure for synthesis of compounds 17 and 18. Potassium selenocyanate (260 mg, 1.8 mmol) was added to a cooled to 0 °C (an ice bath) solution of thiaselenole 8 (440 mg, 1.8 mmol) in MeCN (1.2 mL) with stirring. The mixture was stirred at ~0 °C for 1 h and the solvent was removed under reduced pressure at ~0 °C. A cooled to ~0 °C solution of allyl or 2-propynyl halides (2 mmol) in chloroform (1.5 mL) and tetrabutylammonium bromide (18 mg, 3% mol) were added to the residue followed by the dropwise addition of a cooled to ~0 °C (an ice bath) solution of NaBH4 (0.104 g, 2.7 mmol) in degassed water (1 mL) under an argon atmosphere. The mixture was stirred for 90 min at ~0 °C on the ice bath, then the ice bath was removed and the mixture was stirred for 30 min while warming to room temperature. Degassed water (3 mL) was added and the reaction mixture was extracted with methylene chloride (3 × 10 mL). The organic phase was dried over Na2SO4 and the solvent was removed by a rotary evaporator. The residue was dried in vacuum giving the products 17 and 18.
Allyl 2,3-dihydro-1,4-thiaselenin-2-yl selenide (17). Yield: 500 mg (98%), a light-yellow oil. 1H-NMR (400 MHz, CDCl3): δ 3.22 (1H, dd, 2J = 12.0 Hz, 3J = 10.0 Hz, CH2Se in cycle), 3.32 (1H, dd, 2J = 13.6 Hz, 3J = 8.1 Hz, CH2Se), 3.42 (1H, dd, 2J = 13.6 Hz, 3J = 6.1 Hz, CH2Se), 3.47 (1H, dd, 2J = 12.0 Hz, 3J = 2.6 Hz, CH2Se in cycle), 4.33 (1H, dd, 3J = 10.0 Hz, 3J = 2.6 Hz, SCHSe), 5.16 (1H, dd, 3Jcis = 10.2 Hz, 4J = 1.3 Hz, =CH2), 5.20 (1H, dd, 3Jtrans = 17.3 Hz, 4J = 1.3 Hz, =CH2), 5.84 (1H, m, CH=CH2), 6.41 (1H, d, 3J = 9.8 Hz, =CHS), 6.51 (1H, d, 3J = 9.8 Hz, =CHSe).
13C-NMR (100 MHz, CDCl3): δ 25.56 (1JSeC = 61.1 Hz, SeCH2 in cycle), 27.19 (1JSeC = 63.0 Hz, SeCH2), 35.00 (1JSeC = 76.1 Hz, SCHSe), 109.29 (1JSeC = 116.2 Hz, =CHSe), 116.99 (=CH2), 120.07 (=CHS), 134.41 (=CH).
77Se NMR (100 MHz, CDCl3): δ 230.1 (cycle), 385.4.
MS: m/z (%): 284 (12) [M]+, 245(8) 165 (60), 151 (20), 119 (28), 85 (100).
Anal. Calcd for C7H10SSe2: C 29.59; H 3.55; S 11.29; Se 55.58%. Found: C 22.92; H 3.18; S 12.67; Se 61.02%.
2,3-Dihydro-1,4-thiaselenin-2-yl 2-propynyl selenide (18). Yield: 493 mg (97%), a light-yellow oil. 1H-NMR (400 MHz, CDCl3): δ 2.31 (1H, t, 3J = 2.6 Hz, ≡CH), 3.25 (1H, dd, 2J = 11.7 Hz, 3J = 9.2 Hz, CH2Se in cycle), 3.43 (1H, dd, 2J = 15.7 Hz, 4J = 2.6 Hz, CH2Se), 3.60 (1H, dd, 2J = 11.7 Hz, 3J = 2.2 Hz, CH2Se in cycle), 3.64 (1H, dd, 2J = 15.7 Hz, 4J = 2.6 Hz, CH2Se), 4.67 (1H, dd, 3J = 9.2 Hz, 3J = 2.1 Hz, SCHSe), 6.43 (1H, d, 3J = 9.8 Hz, =CHS), 6.55 (1H, d, 3J = 9.8 Hz, =CHSe).
13C-NMR (100 MHz, CDCl3): δ 8.25 (1JSeC = 62.3 Hz, CH2C≡), 25.58 (1JSeC = 63.4 Hz, SeCH2 in cycle), 36.23 (1JSeC = 77.2 Hz, SCHSe), 72.03 (-C≡), 80.48 (≡CH), 109.67 (1JSeC = 116.2 Hz, =CHSe), 119.44 (=CHS).
77Se NMR (100 MHz, CDCl3): δ 220.5 (cycle), 437.0.
MS: m/z (%): 284 (18) [M]+, 218 (4), 165 (100), 151 (18), 85 (100).
Anal. Calcd for C7H8SSe2: C 29.80; H 2.86; S 11.37; Se 55.98%. Found: C 29.90; H 3.05; S 11.11; Se 56.40%.

3.6. Synthesis of the Products 19–21

General procedure for synthesis of the products19–21. Potassium selenocyanate (144 mg, 1 mmol) was added to a cooled to 0 °C (an ice bath) solution of thiaselenole 8 (244 mg, 1 mmol) in MeCN (0.7 mL) with stirring. The mixture was stirred at ~0 °C for 1 h and the solvent was removed under reduced pressure at ~0 °C. A cooled to ~0 °C solution of alkyl acrylates or acrylonitrile (1.2 mmol) in chloroform (0.5 mL) and tetrabutylammonium bromide (19 mg, 6% mol) were added to the residue followed by the dropwise addition of a cooled to ~0 °C (an ice bath) solution of NaBH4 (0.057 g, 1.5 mmol) in degassed water (0.5 mL). The mixture was stirred for 3.5 h at ~0 °C on the ice bath, then the ice bath was removed and the mixture was stirred for 30 min while warming to room temperature. Degassed water (2 mL) was added and the reaction mixture was extracted with methylene chloride (3 × 8 mL). The organic phase was dried over Na2SO4 and the solvent was removed by a rotary evaporator. The residue was dried in vacuum giving the products 19–21.
3-(2,3-Dihydro-1,4-thiaselenin-2-ylselanyl)propanenitrile (19). Yield: 276 mg (93%), light-yellow oil. The total reaction time was 6 h.
1H NMR (400 MHz, CDCl3): 2.87 (2H, m, CH2CN), 2.98–3.12 (1H, m, CH2CH2Se), 3.32 (1H, dd, 2J = 12.0 Hz, 3J = 9.3 Hz, CH2Se in cycle), 3.59 (1H, dd, 2J = 12.0 Hz, 3J = 2.6 Hz, CH2Se in cycle), 4.64 (1H, dd, 3J = 9.3 Hz, 3J = 2.6 Hz, SCHSe), 6.40 (1H, d, 3J = 9.8 Hz, =CHS), 6.54 (1H, d, 3J = 9.8 Hz, =CHSe).
13C-NMR (100 MHz, CDCl3): δ 18.15 (1JSeC = 66.6 Hz, SeCH2 in cycle), 19.81 (CH2CN), 25.56 (1JSeC = 63.2 Hz, CHSeCH2CH2), 35.98 (1JSeC = 77.1 Hz, SCHSe), 109.88 (1JSeC = 116.2 Hz, =CHSe), 118.43 (CN), 119.31 (=CHS).
77Se NMR (100 MHz, CDCl3): δ 227.1 (cycle), 388.9.
MS: m/z (%): 299 (7) [M]+, 165 (5), 151 (100), 107 (5), 85 (25).
Anal. Calcd for C7H9NSSe2: C 28.29; H 3.05; N 4.71; S 10.79; Se 53.15. Found: C 28.07; H 2.93; N 4.58; S 10.56; Se 52.92.
Methyl 3-(2,3-dihydro-1,4-thiaselenin-2-ylselanyl)propanoate (20). Yield: 314 mg (95%), a light-yellow oil. 1H NMR (400 MHz, CDCl3): δ 2.77 (2H, t, 3J = 7.2 Hz, CH2C=O), 2.97 (2H, t, 3J = 6.9 Hz, CH2Se), 3.29 (1H, dd, 2J = 11.5 Hz, 3J = 10.5 Hz, CH2Se in cycle), 3.46 (1H, dd, 2J = 11.5 Hz, 3J = 2.8 Hz, CH2Se in cycle), 3.66 (3H, s, CH3), 4.50 (1H, dd, 3J = 10.5 Hz, 3J = 2.8 Hz, SCHSe), 6.35 (1H, d, 3J = 9.7 Hz, =CHS), 6.43 (1H, d, 3J = 9.7 Hz, =CHSe).
13C-NMR (100 MHz, CDCl3): δ 18.29 (1JSeC = 66.6 Hz, SeCH2 in cycle), 25.47 (1JSeC = 62.5 Hz, CHSeCH2CH2), 35.48 (CH2C=O), 35.49 (1JSeC = 77.4 Hz, SCHSe), 51.69 (CH3), 109.15 (1JSeC = 116.0 Hz, =CHSe), 120.21 (=CHS), 172.12 (CH2C=O).
77Se NMR (100 MHz, CDCl3): δ 233.3 (in cycle), 381.3.
MS: m/z (%): 330 (25) [M]+, 165 (100), 151 (23), 107 (14), 85 (97).
Anal. Calcd for C8H12O2SSe2: C 29.10; H 3.66; S 9.71, Se 47.83%. Found: C 29.22; H 3.38; S 9.67, Se 48.11%.
Ethyl 3-(2,3-dihydro-1,4-thiaselenin-2-ylselanyl)propanoate (21). Yield: 330 mg (96%), a light-yellow oil. 1H NMR (400 MHz, CDCl3): δ 1.35 (3H, t, 3J = 7.2 Hz, CH3CH2), 2.82 (2H, t, 3J = 7.2 Hz, CH2C=O), 3.04 (2H, m, CH2Se), 3.36 (1H, dd, 2J = 11.7 Hz, 3J = 9.9 Hz, CH2Se in cycle), 3.53 (1H, dd, 2J = 11.7 Hz, 3J = 2.5 Hz, CH2Se in cycle), 4.19 (2H, q, 2J = 7.2 Hz, CH2CH3), 4.57 (1H, д.д, 3J = 9.9 Hz, SCHSe), 6.42 (1H, d, 3J = 9.7 Hz, =CHS), 6.49 (1H, d, 3J = 9.7 Hz, =CHSe).
13C-NMR (100 MHz, CDCl3): δ 14.18 (CH3), 18.51 (1JSeC = 66.0 Hz, CHSeCH2CH2), 25.59 (1JSeC = 62.9 Hz, SeCH2), 35.61 (CH2C=O), 35.86 (SCHSe), 60.79 (OCH2CH3), 109.22 (1JSeC = 115.5 Hz, =CHSe), 120.42 (=CHS), 171.87 (CH2C=O).
77Se NMR (100 MHz, CDCl3): δ 233.4 (in cycle), 380.9.
MS: m/z (%): 346 (24) [M]+, 165 (100), 151 (50), 125 (1), 85 (76).
Anal. Calcd for C9H14O2SSe2: C 31.41; H 4.10; S 9.32, Se 45.88%. Found: C 31.33; H 4.08; S 9.25, Se 46.12%.

3.7. Synthesis of Alkyl (Z)-3-(2,3-Dihydro-1,4-thiaselenin-2-ylselanyl)acrylates

General procedure for the synthesis of the products 22 and 23. Potassium selenocyanate (173 mg, 1.2 mmol) was added to a cooled to 0 °C (an ice bath) solution of thiaselenole 8 (293 mg, 1.2 mmol) in MeCN (1 mL) with stirring. The mixture was stirred at ~0 °C for 1 h and the solvent was removed under reduced pressure at ~0 °C. A cooled to ~0 °C solution of alkyl propiolates (1.5 mmol) in chloroform (1 mL) and tetrabutylammonium bromide (24 mg, 6% mol) were added to the residue followed by the dropwise addition of a cooled to ~0 °C (an ice bath) solution of NaBH4 (0.07 g, 1.84 mmol) in degassed water (0.7 mL). The mixture was stirred for 2.5 h at ~0 °C on the ice bath, then the ice bath was removed and the mixture was stirred for 30 min while warming to room temperature. Degassed water (2 mL) was added and the reaction mixture was extracted with methylene chloride (3 × 10 mL). The organic phase was dried over Na2SO4 and the solvent was removed by a rotary evaporator. The residue was dried in vacuum giving the products 22 and 23.
Methyl (Z)-3-(2,3-dihydro-1,4-thiaselenin-2-ylselanyl)acrylate (22). Yield: 386 mg (98%), a light-yellow oil.
1H NMR (400 MHz, CDCl3): δ 3.32 (1H, dd, 2J = 11.9 Hz, 3J = 9.7 Hz, CH2Se), 3.48 (1H, dd, 2J = 11.9 Hz, 3J = 2.6 Hz, CH2Se), 3.71 (3H, s, CH3), 4.48 (1H, dd, 2J = 9.7 Hz, 3J = 2.6 Hz, SCHSe), 6.35 (1H, d, 3J = 9.5 Hz, SeCH=CHC=O), 6.37 (1H, d, 3J = 9.8, =CHS), 6.46 (1H, d, 3J = 9.8 Hz, =CHSe), 7.76 (1H, d, 3J = 9.5 Hz, SeCH=CHC=O).
13C NMR (100 MHz, CDCl3): δ, 13C NMR (100 MHz, CDCl3): δ 25.00 (1JSeC = 62.1 Hz, SeCH2), 37.67 (1JSeC = 71.1 Hz, SCHSe), 51.63 (CH3), 109.66 (1JSeC = 116.8 Hz, =CHSe), 117.54 SeCH=CHC=O, 119.86 (=CHS), 144.18 (1JSeC = 137.1 Hz, SeCH=CHC=O), 167.62 (CH2C=O).
77Se NMR (76 MHz, CDCl3): δ 231.9 (in cycle), 548.0.
MS (EI), m/z (%): 330 (11) [M]+, 251(6), 191(5), 165 (100), 151 (6), 85 (74).
Anal. Calcd for C8H10O2SSe2: C 29.38; H 3.07; S 9.77; Se 48.12%. Found: C 29.64; H 2.95; S 9.48; Se 47.83%.
Ethyl (Z)-3-(2,3-dihydro-1,4-thiaselenin-2-ylselanyl)acrylate (23). Yield: 399 mg (97%), a light-yellow oil.
1H NMR (400 MHz, CDCl3): 1.30 (3H, t, 3J = 7.2 Hz, CH3CH2), 3.34 (1H, dd, 2J = 11.9 Hz, 3J = 9.7 Hz, CH2Se), 3.48 (1H, dd, 2J = 11.9 Hz, 3J = 2.6 Hz, CH2Se), 4.18 (2H, q, 2J = 7.2 Hz, CH2CH3), 4.47 (1H, dd, 2J = 9.7 Hz, 3J = 2.6 Hz, SCHSe), 6.35 (1H, d, 3J = 9.5 Hz, SeCH=CHC=O), 6.36 (1H, d, 3J = 9.8 Hz, =CHS), 6.47 (1H, d, 3J = 9.8 Hz, =CHSe), 7.75 (1H, d, 3J = 9.5 Hz, SeCH=CHC=O).
13C NMR (100 MHz, CDCl3): δ, 13C NMR (100 MHz, CDCl3): δ 13.97 (CH3), 24.80 (1JSeC = 71.9 Hz, SeCH2), 37.43 (1JSeC = 70.0 Hz, SCHSe), 60.41 (OCH2CH3), 109.48 (1JSeC = 116.8 Hz, =CHSe), 117.59 (SeCH=CHC=O), 119.47 (=CHS), 143.86 SeCH=CHC=O), 167.06 (C=O).
77Se NMR (76 MHz, CDCl3): δ 231.9 (in cycle), 546.6.
MS (EI), m/z (%): 343 (24) [M]+, 165 (100), 151 (50), 125 (1), 85 (76).
Anal. Calcd for C9H12O2SSe2: C 31.59; H 3.53; S 9.37; Se 46.15%. Found: C 31.74; H 3.71; S 9.28; Se 44.79%.

4. Conclusions

The regio- and stereoselective one-pot synthesis of a novel family of 2,3-dihydro-1,4-thiaselenin-2-yl selenides has been developed based on trapping intermediate dihydro-1,4-thiaselenin-2-yl selenolate anion at low temperature. The latter was generated from dihydro-1,4-thiaselenin-2-yl selenocyanate by the action of sodium borohydride and involved in nucleophilic substitution and addition reactions to activated double and triple bond under phase transfer catalysis conditions. The nucleophilic substitution reactions with alkyl halides give alkyl, allyl and propargyl 2,3-dihydro-1,4-thiaselenin-2-yl selenides in 93–98% yields. The addition reactions of dihydro-1,4-thiaselenin-2-yl selenolate anion to alkyl acrylates, acrylonitrile and alkyl propiolates proceed in a regio- and stereoselective fashion to afford 2,3-dihydro-1,4-thiaselenin-2-yl selenides, containing alkyl propanoates, cyanoethyl and alkyl propenoate groups, in high yields. It should be emphasized that not a single representative of 2,3-dihydro-1,4-thiaselenin-2-yl selenides has been previously described in the literature.
The obtained products are valuable intermediates for organic synthesis and compounds with putative biological activity. It is known that the 1,4-thiaselenine derivatives exhibit antibacterial and antifungal activities [18].

Supplementary Materials

The following supporting information can be downloaded at: https://www.mdpi.com/article/10.3390/catal12101236/s1, 1H, 13C, and 77Se NMR spectra of the products.

Author Contributions

Methodology and the data curation, S.V.A.; investigation and research experiments, A.S.F.; conceptualization and the paper preparation, V.A.P.; NMR investigation, A.I.A. 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 for structural investigations.

Conflicts of Interest

The authors declare no conflict of interest.

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Catalysts 12 01236 g001 550
Figure 1. Examples of six-membered selenium heterocycles of practical importance: 2-(4-chlorophenyl)-6-phenyl-2,3-dihydro-1,4-oxaselenine-1,4-dione (1), 7-(4-methyl-6-oxo-1,4,5,6-tetrahydro-3-pyridazinyl)-2H-1,4-benzoselenazin-3(4H)-one (2), quino[2’,3’:5,6][1,4]thiaselenino[3,2-b]quinoline (3), 1-(1,4-selenazinan-4-ymethyl)-dihydro-1H-pyrrole-2,5-dione (4), 4-methyl-2-(4-methylphenyl)-6-propyl-5,6-dihydro-4H-1,3-selenazin-4-ol (5), 2-aryl-6-phenyl-1,4-oxaselenines (6), and 4-methyl-2-phenyl-5,6-dihydro-4H-1,3-selenazin-4-ol (7) [13,14,15,16,17,18,19].
Figure 1. Examples of six-membered selenium heterocycles of practical importance: 2-(4-chlorophenyl)-6-phenyl-2,3-dihydro-1,4-oxaselenine-1,4-dione (1), 7-(4-methyl-6-oxo-1,4,5,6-tetrahydro-3-pyridazinyl)-2H-1,4-benzoselenazin-3(4H)-one (2), quino[2’,3’:5,6][1,4]thiaselenino[3,2-b]quinoline (3), 1-(1,4-selenazinan-4-ymethyl)-dihydro-1H-pyrrole-2,5-dione (4), 4-methyl-2-(4-methylphenyl)-6-propyl-5,6-dihydro-4H-1,3-selenazin-4-ol (5), 2-aryl-6-phenyl-1,4-oxaselenines (6), and 4-methyl-2-phenyl-5,6-dihydro-4H-1,3-selenazin-4-ol (7) [13,14,15,16,17,18,19].
Catalysts 12 01236 g001
Catalysts 12 01236 sch001 550
Scheme 1. The reactions of 2-bromomethyl-1,3-thiaselenole with thiocyanate and selenocyanate nucleophiles.
Scheme 1. The reactions of 2-bromomethyl-1,3-thiaselenole with thiocyanate and selenocyanate nucleophiles.
Catalysts 12 01236 sch001
Catalysts 12 01236 sch002 550
Scheme 2. The generation of sodium 2,3-dihydro-1,4-thiaselenin-2-yl selenolate 13 from intermediate 2,3-dihydro-1,4-thiaselenin-2-yl selenocyanate 12 at low temperature (0 °C).
Scheme 2. The generation of sodium 2,3-dihydro-1,4-thiaselenin-2-yl selenolate 13 from intermediate 2,3-dihydro-1,4-thiaselenin-2-yl selenocyanate 12 at low temperature (0 °C).
Catalysts 12 01236 sch002
Catalysts 12 01236 sch003 550
Scheme 3. The synthesis of dihydro-1,4-thiaselenin-2-yl propyl selenide 14 from thiaselenole 8 under phase transfer catalysis conditions.
Scheme 3. The synthesis of dihydro-1,4-thiaselenin-2-yl propyl selenide 14 from thiaselenole 8 under phase transfer catalysis conditions.
Catalysts 12 01236 sch003
Catalysts 12 01236 sch004 550
Scheme 4. The obtained (1,2-dihydro-1,4-thiaselenin-2-yl) selenides 14–23 and the 77Se-NMR data (colored in blue, ppm).
Scheme 4. The obtained (1,2-dihydro-1,4-thiaselenin-2-yl) selenides 14–23 and the 77Se-NMR data (colored in blue, ppm).
Catalysts 12 01236 sch004
Table
Table 1. The synthesis of the products 14–23 based on thiaselenole 1, potassium selenocyanate and electrophilic reagents under phase transfer catalysis conditions.
Table 1. The synthesis of the products 14–23 based on thiaselenole 1, potassium selenocyanate and electrophilic reagents under phase transfer catalysis conditions.
Catalysts 12 01236 i001
RunsStarting CompoundDuration
(h)		TBAB
(mol%)		ProductYield (%)
1Propyl bromide431498%
2Methyl iodide431593%
3Ethyl bromide431696%
4Allyl bromide331798%
5Propargyl bromide331897%
6Acrylonitrile661993%
7Methyl acrylate562095%
8Ethyl acrylate562196%
9Methyl propiolate462298%
10Ethyl propiolate462397%
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Amosova, S.V.; Filippov, A.S.; Potapov, V.A.; Albanov, A.I. Regio- and Stereoselective One-Pot Synthesis of New Heterocyclic Compounds with Two Selenium Atoms Based on 2-Bromomethyl-1,3-thiaselenole Using Phase Transfer Catalysis. Catalysts 2022, 12, 1236. https://doi.org/10.3390/catal12101236

AMA Style

Amosova SV, Filippov AS, Potapov VA, Albanov AI. Regio- and Stereoselective One-Pot Synthesis of New Heterocyclic Compounds with Two Selenium Atoms Based on 2-Bromomethyl-1,3-thiaselenole Using Phase Transfer Catalysis. Catalysts. 2022; 12(10):1236. https://doi.org/10.3390/catal12101236

Chicago/Turabian Style

Amosova, Svetlana V., Andrey S. Filippov, Vladimir A. Potapov, and Alexander I. Albanov. 2022. "Regio- and Stereoselective One-Pot Synthesis of New Heterocyclic Compounds with Two Selenium Atoms Based on 2-Bromomethyl-1,3-thiaselenole Using Phase Transfer Catalysis" Catalysts 12, no. 10: 1236. https://doi.org/10.3390/catal12101236

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