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Review

Recent Advances in Design and Synthesis of 1,3-Thiaselenolane and 1,3-Thiaselenole Derivatives

by
Svetlana V. Amosova
* and
Nataliya A. Makhaeva
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), 1221; https://doi.org/10.3390/catal13081221
Submission received: 7 July 2023 / Revised: 6 August 2023 / Accepted: 15 August 2023 / Published: 17 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

:
Recent advances in the design and synthesis of five-membered heterocycles containing both sulfur and selenium atoms—1,3-thiaselenolane and 1,3-thiaselenole derivatives—are discussed in this review. These heterocyclic systems are of interest as intermediates for organic synthesis and compounds that can exhibit various useful properties, including biological activity and electrical conductivity. The main focus of the review is on the works of the last 20 years that make use of catalytic reactions. Synthetic methods for the preparation of structurally related 1,4,5,8-diselenadithiafulvalenes based on catalytic cross-coupling reactions are also presented. To date, the design and synthesis of 1,3-thiaselenolane and 1,3-thiaselenole derivatives have not been discussed in a separate review.

Graphical Abstract

1. Introduction

After the discovery of the important biological role of selenium, organoselenium chemistry began to develop rapidly. A number of classes of the organoselenium compounds have acquired great significance [1,2,3,4,5]. In terms of practical use, selenium heterocycles are particularly noteworthy. These compounds find applications in different fields of our lives, such as biology, medicine, pharmaceuticals, and material sciences, including various aspects of fundamental organic chemistry [1,2,3,4,5].
A number of selenium heterocycles exhibit glutathione peroxidase-like properties and can be used to treat diseases caused by oxidative stress, such as cardiovascular, ischemic stroke, Parkinson’s, and Alzheimer’s disease [6,7,8,9,10,11,12]. Some selenium heterocyclic and functionalized compounds are considered potential anti-cancer drugs [13,14,15,16,17,18,19,20,21] and exhibit antidepressant [22,23,24,25,26] and antiviral activities [27], including anti-HIV [28] and anti-SARS-CoV-2 properties [29,30,31] (Figure 1). Ebselen, an anti-inflammatory drug with neuroprotective and glutathione peroxidase-like properties, is undergoing clinical trials in several areas, including the treatment of COVID-19 [6,7,29].
This review covers design and synthetic methods for the preparation of 1,3-thiaselenolane and 1,3-thiaselenole derivatives (Figure 2) since January 2000, with an emphasis on catalytic reactions. This class of compounds is relatively few in number but very important.
Film composites based on linear and branched polymers containing the 1,3-thiaselenole ring in their structure exhibit photoconductivity [32,33] and can be used as efficient recording media [34,35]. Materials based on 1,3-diselenafulvene derivatives and their analogues show magnetic [36,37,38,39], conductive [40,41,42], and optical properties [43,44,45] (Figure 2) and can find a large number of technological applications [46,47].
Catalysts 13 01221 g001
Figure 1. Selenium heterocyclic and functionalized compounds with biological activity [3,6,8,10,12,18,22,28,29,30].
Figure 1. Selenium heterocyclic and functionalized compounds with biological activity [3,6,8,10,12,18,22,28,29,30].
Catalysts 13 01221 g001
Catalysts 13 01221 g002
Figure 2. Examples of 1,3-thiaselenolane and 1,3-thiaselenole derivatives and their practical applications [37,40,44,45].
Figure 2. Examples of 1,3-thiaselenolane and 1,3-thiaselenole derivatives and their practical applications [37,40,44,45].
Catalysts 13 01221 g002
1,3-Thiaselenolane and 1,3-thiaselenole derivatives include not only biologically active compounds, but also various conducting materials based on structurally related 1,4,5,8-diselenadithiafulvalenes. Synthetic methods for the preparation of 1,4,5,8-diselenadithiafulvalenes are based on catalytic cross-coupling reactions. Moreover, 1,3-thiaselenolane and 1,3-thiaselenole derivatives have not previously been discussed in a separate review.

2. 1,3-Thiaselenolane and 1,3-Thiaselenole Derivatives

2.1. 1,3-Thiaselenolane and 1,3-Thiaselenole Derivatives Based on Selenium Dihalides

A noticeable trend in the development of organoselenium chemistry in the last two decades is the use of new electrophilic reagents, selenium dichloride and dibromide, in the synthesis of organoselenium compounds.
Previously, selenium dihalides were studied by UV-visible, photoelectron, Raman, and 77Se NMR spectroscopy, and it was shown that these reagents exist in equilibrium with other selenium species (selenium monohalides and selenium tetrahalides) in solutions and cannot be isolated in pure form [48,49,50,51].
However, it was found that freshly prepared selenium dichloride and dibromide can be used for the selective preparation of organoselenium compounds, and these reagents were successfully introduced into organic synthesis [52,53,54,55]. The first synthesis of organoselenium compounds from selenium dichloride and dibromide is the preparation of 1,4-selenasilafulvenes by the cyclization reaction of these reagents with dimethyldiethynylsilane [52]. The selectivity and efficiency of the use of selenium dichloride and dibromide in organic synthesis have been shown in many reactions, which made it possible to obtain previously unknown classes of organoselenium compounds and study their chemical properties [53,54,55,56,57,58,59,60,61,62,63,64,65,66]. Compounds with high glutathione peroxidase-like activity have been found [56].
New synthetic approaches have been developed using the chemistry of these reagents. A new methodology for the synthesis of fused heterocyclic selenium compounds is based on the annulation and annulation/functionalization reactions of selenium dihalides with aromatic and natural compounds [57,58]. Another general regioselective approach to new selenium-containing heterocyclic compounds is based on addition/bis-functionalization reactions of selenium dibromide with alkenes in the presence of nucleophilic reagents [59,60]. Using this approach, a one-pot synthesis of novel, functionalized organoselenium compounds by bis-alkoxyselenenylation of alkenes with selenium dibromide and alcohols has been developed [59]. An efficient regioselective synthesis of novel, functionalized organoselenium compounds by cyclofunctionalization reactions of selenium dihalides with natural compounds and their derivatives has also been realized [61].
The use of selenium dichloride and dibromide made it possible to discover new possibilities in organic synthesis [53,54,55,56,57,58,59,60,61,62,63,64,65,66]. The reaction of selenium dichloride with divinyl sulfide at −50 °C in chloroform gave six-membered heterocycle, 2,6-dichloro-1,4-thiaselenane (1) (a 6/1 diastereomer ratio), in quantitative yield, which underwent rearrangement (chloroform, room temperature) to a five-membered heterocycle, 5-chloro-2-chloromethyl-1,3-thiaselenolane (2) in 61% yield (a 2/1 diastereomer ratio). Along with thiaselenolane 2, its dehydrochlorination product, 2-chloromethyl-1,3-thiaselenole (3), was formed in the reaction mixture in 36% yield (Scheme 1) [63,64,65,66].
Granular elemental selenium, powdered immediately before the reaction, and freshly distilled sulfuryl chloride were used to prepare selenium dichloride.
Treatment of thiaselenane 1 with pyridine in chloroform gave only thiaselenole 3 in 95% yield (Scheme 1) [63,64,65,66].
The reaction of selenium dichloride with divinyl sulfide at room temperature gave a product mixture: thiaselenane 1 (a 3/1 diastereomer ratio, 72% yield) and thiaselenolane 2 (a 1/1 diastereomer ratio, yield 24%). Pure thiaselenole 3 in 30% yield was successfully obtained by the distillation of this reaction mixture (Scheme 1) [63,64,65,66].
The reaction route of selenium dichloride with divinyl sulfide was shown based on the quantum chemical calculations [65]. The reaction route includes the initial formation of thiaselenane 1, the rearrangement of thiaselenane 1 into thiaselenolane 2, and the dehydrochlorination of product 2 into thiaselenole 3 (Scheme 1). The results of the quantum chemical calculations are in excellent agreement with experimental data [65].
Divinyl sulfide is a multifaceted starting material for the synthesis of a variety of organosulfur compounds, including heterocycles [67,68].
The reaction of selenium dibromide with divinyl sulfide in chloroform at room temperature led to the formation of 5-bromo-2-bromomethyl-1,3-thiaselenolane (4) in 78% yield in the form of a mixture of diastereomers in a 3/2 ratio and 2-bromomethyl-1,3-thiaselenole (5) (17% yield). It was shown that thiaselenole 5 was formed as the product of the spontaneous dehydrobromination of thiaselenolane 4 (Scheme 2) [69,70].
Selenium dibromide was obtained in situ by the reaction of selenium powder with bromine in chloroform or carbon tetrachloride. The resulting solution of selenium dibromide and a freshly prepared solution of divinyl sulfide were simultaneously added dropwise to the reaction flask.
However, when this reaction was carried out at −55 °C, it was possible to fix the formation of the intermediate six-membered heterocycle 2,6-dibromo-1,4-thiaselenane (6), which was spontaneously rearranged into heterocycles 4 and 5 (Scheme 2) [69,70].
As it turned out, the nature of the solvent is very important for the reaction of selenium dibromide with divinyl sulfide, and the rates of rearrangement and dehydrobromination depend on the polarity of the solvent. Replacing the solvent with nonpolar carbon tetrachloride made it possible to obtain intermediate six-membered thiaselenane 6 in quantitative yield, which was stable for several days at −20 °C in solution. Thiaselenane 6 underwent spontaneous rearrangement into a five-membered isomer: 5-bromo-2-bromomethyl-1,3-thiaselenolane (4) in quantitative yield, when removing the solvent from the reaction mixture. The addition of pyridine to the reaction mixture with thiaselenane 6 significantly accelerated the rearrangement of this compound into the five-membered heterocycle 4 and its dehydrobromination to thiaselenole 5 in 95% yield (Scheme 3) [70,71,72]. It is known that pyridine can act not only as a dehydrohalogenation agent but also as a catalyst [73].
2-Bromomethyl-1,3-thiaselenole (5) is a unique reagent in which the high anchimeric assistance effect of the selenium atom allows this compound to exhibit unusual properties in nucleophilic reactions. This effect, also known as the neighboring group participation, is usually considered as a factor accelerating the rate of nucleophilic substitution reactions. In this case, the anchimeric effect leads to new rearrangements with the selective formation of various selenium-containing heterocyclic compounds.
The structure of thiaselenole 5 suggests the possibility of the formation of both seleniranium and thiiranium cations, whose participation in the nucleophilic substitution reaction can lead to the formation of two different reaction products (Scheme 4).
However, in this case, the reaction proceeds via an intermediate seleniranium cation. This is explained by the high anchimeric assistance effect of the selenium atom, which significantly exceeds the effect of the sulfur atom. This superiority of the selenium atom was established based on the determination of the absolute and relative rates of nucleophilic substitution of chlorine in selenium- and sulfur-containing analogs, 2,6-dichloro-9-selenabicyclo [3.3.1]nonane and 2,6-dichloro-9-thiabicyclo [3.3.1]nonane [74].
The reaction of thiaselenole 5 with ammonium thiocyanate in acetonitrile at room temperature led to the formation of only 2,3-dihydro-1,4-thiaselenin-2-yl thiocyanate (7) in 95% yield. However, at 60 °C, a complete rearrangement of the heterocycle 7 into the thermodynamic product of the reaction, five-membered (1,3-thiaselenole-2-yl)methylthiocyanate (8), took place (Scheme 5) [75,76,77].
An unusual result was obtained when thiaselenole 5 interacted with potassium selenocyanate in acetonitrile at room temperature (5 min). As a result of the reaction, five-membered 1,3-thiaselenol-2-yl-methyl selenocyanate (9) was formed in quantitative yield (Scheme 5) [75,76,77]. Product 9 was easily separated from the reaction mixture by filtering the solution and removing the solvent at reduced pressure without additional purification. At the same time, using 1H NMR monitoring under the same conditions, but at 0 °C, the intermediate six-membered selenocyanate 10 was successfully fixed, which, over time and with increasing temperature, rearranged into the thermodynamic product five-membered heterocycle 9 (Scheme 5) [75,76,77].
The formation of dihydrothiaselenines 7,10 occurs through an intermediate seleniranium cation arising as a result of the anchimeric effect of the selenium atom. The further reaction includes the substitution of the bromide anion with the thiocyanate anion that attacks the carbon atom with the cleavage of the CH–Se bond and the opening of the seleniranium cation (Scheme 5) [75,76,77]. Thus, the five-membered heterocycle is expanded into a six-membered one.
The formation of heterocycles 8,9 occurs as a rearrangement of dihydrothiaselenines 7,10, also proceeding through the seleniranium intermediate, and the thiocyanate or selenacyanate anion attacks the carbon atom of the CH2 group in the seleniranium cation. In this case, the cleavage in the Se–CH2 bond leads to a contraction of the six-membered ring to a five-membered one (Scheme 5) [75,76,77]. Thus, the formation of thiocyanate 8 and selenocyanate 9 is the result of two rearrangements, rather than a “classical” nucleophilic substitution of the bromine atom in thiaselenole 5.
When heterocycle 9 was treated with potassium hydroxide in methanol, bis(1,3-thiaselenol-2-yl methyl) diselenide (11) was formed in 90% yield, consisting of two diastereomers (Scheme 5) [75,76,77].
Compounds 7–11 are perspective intermediates for organic synthesis with possible biological activity. Unsaturated selenocyanate 9 and diselenide 11 were used for the synthesis of new ensembles of S/Se-containing heterocycles with promising biological activity [77].
The reaction of NaBH4 with selenocyanate 9 or diselenide 11 in methanol at room temperature afforded sodium 1,3-thiaselenol-2-ylmethylselenolate, which was in situ involved in nucleophilic substitution reactions with organohalogen compounds, bearing alkyl, benzyl, allyl, 2-propynyl, 2-pyridylmethyl, and 4-fluorobenzyl groups. The products 1,3-thiaselenol-2-ylmethyl selenides 12a–l were obtained in high yields (75–92%) and in a regioselective manner (Scheme 6) [77].
However, the method of the generation of the 1,3-thiaselenol-2-ylmethylselenolate anion from selenocyanate 9 was slightly more effective, and the yields of the thiaselenol-2-ylmethylselanyl derivatives 12a–l from selenocyanate 9 were higher compared to that of the method based on diselenide 11 (Scheme 6) [77].
The 1,3-Thiaselenol-2-ylmethylselenolate anion, obtained from selenocyanate 9, was also used in the nucleophilic addition reaction to activate acetylenes including alkyl propiolates. The reaction was carried out in methanol at 0 °C. For example, alkyl 3-[(1,3-thiaselenol-2-ylmethyl)selanyl]-2-propenoates 13a (Z/E = 94/6) and 13b (Z/E = 93/7) were obtained in a regio- and stereoselective fashion in 94% and 90% yields, respectively (Scheme 7) [77].
The reaction of the nucleophilic substitution of 2-bromomethyl-1,3-thiaselenole (5) with mercapto benzazoles 14a–d, containing various combinations of heteroatoms (N, O and S), produced the corresponding 2,3-dihydro-1,4-thiaselenins 15a–d and 1,3-thiaselenole derivatives 16a–d in quantitative yields. The reaction proceeded in dimethylformamide or acetonitrile in the presence of bases such as lithium or potassium carbonate (Scheme 8) [78,79].
It is known that metal carbonates can be used not only as dehydrobrominating but also as catalytic reagents [80,81,82,83,84]. In this case, six-membered products 15a–d were rearranged into more stable thermodynamic five-membered products 16a–d under the action of lithium or potassium carbonate. This was shown by the example of compound 16a, which was obtained by heating compound 15a to 90 °C for 1 h (Scheme 8) [78,79].
It is known that imidazole and pyrazole derivatives exhibit fungicidal activity [85], and selenium-containing benzoxazoles act as both bactericides and fungicides [86].
Since selenium compounds exhibit glutathione peroxidase-like properties, the authors of [87] attempted to obtain hybrid molecules combining imidazole and selenium heterocycles.
The nucleophilic substitution reaction of 2-bromomethyl-1,3-thiaselenole (5) with 1-methyl-1H-imidazole-2-thiol 17 in dimethylformamide in the presence of potassium carbonate at room temperature produced 2-(2,3-dihydro-1,4-thiaselenin-2-ylsulfanyl)-1-methyl-1H-imidazole (18) in 80% yield (Scheme 9) [87].
The reaction proceeded with the expansion of the cycle, accompanied by a rearrangement with the formation of a functionalized 2,3-dihydro-1,4-thiaselenin ring. The reaction proceeded in a regioselective fashion; the five-membered products were not detected, even as traces.
It can be assumed that the nucleophilic substitution of thiaselenole 5 by imidazole 17 in dimethylformamide involves the formation of seleniranum intermediate. Next, a nucleophilic attack occurs on the C2 atom of seleniranum cations, leading to the breaking of the Se–C2 bond, the expansion of the ring to 2,3-dihydro-1,4-thiaselenine, and the formation of product 18 (Scheme 10) [87].
Imidazole 18 was rearranged into 1-methyl-2-[(1,3-thiaselenol-2-yl methyl)sulfonyl]-1H-imidazole (19) with ring constriction when boiled in chloroform solution. In this case, 1-(2,3-dihydro-1,4-thiaselenin-2-yl)-3-methyl-1,3-dihydro-2H-imidazole-2-thione 20 was also formed (Scheme 9) [87].
When this reaction was carried out in acetonitrile in the absence of a base at room temperature, a hydrobromide of compound 18 was formed, 2-(2,3-dihydro-1,4-thiaselenin-2-ylsulfanyl)-1-methyl-1H-imidazole-3-ium bromide (21), in 52% yield, which was completely isomerized into the thermodynamic product, 1-methyl-2-[(1,3-thiaselenol-2-ylmethyl)sulfanyl]-1H-imidazole-3-ium bromide (22) (yield 96%) in a methanol solution at room temperature. Thiaselenole 22, in turn, was easily dehydrobrominated and converted into thiaselenole 19 after treatment with an aqueous solution of potassium hydroxide in 95% yield (Scheme 9) [87].
The nucleophilic substitution reaction of thiaselenole 5 with 5-methyl-1,3,4-thiadiazole-2-thiol (23) in acetonitrile at room temperature and subsequent treatment of the reaction mixture with sodium hydrocarbonate provided 2-methyl-5-{[(1,3-thia-selenol-2-yl)methyl]sulfanyl}-1,3,4-thiadiazole (24) in 43% yield. The formation of product 24 presumably proceeded through a double rearrangement with the expansion and contraction of the thiaselenole ring. The intermediate six-membered product 25 was detected by 1H NMR spectroscopy in a non-salt form during the treatment of the reaction mixture with sodium hydrocarbonate at the initial stage of the reaction (Scheme 11) [88].
Thus, the high anchimeric assistance effect of the selenium atom in thiaselenole 5 is the driving force for the formation of seleniranium intermediate. Over the past fifteen years, a fundamental approach has been developed surrounding the regio- and stereoselective synthesis of functionalized organoselenium heterocyclic compounds based on nucleophilic substitution reactions proceeding via intermediate seleniranium cation.
Sulfur- and selenium-containing heterocycles 16a–d,19,22,24, functionalized with pharmacophore nitrogen heterocycles, are promising, biologically active heterocyclic systems with a wide spectrum of activity, including glutathione peroxidase-like activity (Scheme 8, Scheme 9, Scheme 10 and Scheme 11) [78,79,87,88].
The analysis of the literature data has shown that 2-bromomethyl-1,3-thiaselenole (5) is a unique and promising reagent for organic synthesis that exhibits unusual properties in nucleophilic substitution and addition reactions [63,64,65,66,69,70,71,72,75,76,77,78,79,87,88].

2.2. 1,3-Thiaselenolanes Based on Catalytic Reactions

Tetrabutylammonium fluoride (TBAF) is used in ring-opening reactions [89,90] and catalyzes the reactions of substituted epoxides with hexamethyldisilathiane (HMDST) [91] and hexamethyldisilaselenane [90], providing a direct and simple access to β-mercaptoalcohols and β-functionalized selenols, respectively, in a highly regio- and stereoselective way. Alkyl selenols can easily react with electrophiles, such as alkyl halides, acyl chlorides, and strained heterocycles to obtain the corresponding functionalized selenides under very mild conditions [90].
The reaction of a three-membered episulfide, 2-methylthiirane 27 with hexamethyldisilaselenane 28 was carried out in the presence of tetrabutylammonium fluoride as a catalyst and 1-bromo-1-methoxyethane 29. In this case, 1,3-thiaselenolane 30 was obtained in a 70/30 diastereomer ratio, which formed as a result of the capture of the intermediate product β-mercapto diselenide by bromine derivative 29 in situ (Scheme 12) [92].
Lewis acids can be used for effecting Michael-type addition reactions. Aluminum oxide as a catalyst [93,94] and a catalytic system aluminum oxide/potassium fluoride [95,96,97,98] were used in these reactions.
Mercapto-substituted alkyl-vinyl selenides 32a,b were obtained by the reaction of seleno-Michael addition of substituted β-mercapto-selenol 31b to electron-deficient alkenes in toluene solution in the presence of aluminum oxide (Scheme 13) [99]. Although β-mercapto-selenol 31b contains mercapto and selenol groups, only the latter was involved in the addition reaction. Product 32a was obtained in 79% yield as a mixture of diastereomers (a 90/10 ratio).
Vinyl selenide 32b was generated in situ and involved in the cyclization reaction under the same conditions (Scheme 13) [99]. The strong nucleophilic character of the mercapto fragment of the α,β-unsaturated γ-selenoesters 32a,b provided access to disubstituted 1,3-thiaselenolanes 33a,b by means of thia-Michael intramolecular reactions occurring in the presence of triethylamine for the preparation of compound 33a (92% yield, dr = 51/49), and aluminum oxide in the case of compound 33b (83% yield, dr = 55/49) (Scheme 13) [99]. This method of vinyl selenides synthesis is very convenient, since the reaction proceeds under mild conditions and without the use of transition metal catalysts.
The functionalized 1,3-thiaselenolanes 33a,b, containing sulfur and selenium in their structure, exhibit antioxidant activity and peroxidase-like properties [99].
Quite a lot of methods for the synthesis of vinyl selenides have been developed by catalyzed addition reactions of organic diselenides and selenolate to the triple bond of acetylenes [100,101,102]. Vinyl selenides are valuable intermediates for organic synthesis. Vinyl selenides were successfully used as starting compounds for the stereoselective preparation of functionalized ethenes by cross-coupling reactions and for a variety of other useful transformations [100,101,102].
Iodine-mediated cyclization is known to be a valuable tool for the creation of various heterocycles by the intramolecular cyclization of unsaturated carbon–carbon bond with various nucleophilic reagents such as nitrogen-, oxygen-, sulfur- [103,104,105,106,107] and selenium-centered [108,109,110] nucleophiles.
Isoselenocyanates 34a–d were synthesized by the reactions of N-substituted formamides with an excess of triphosgene, selenium powder, and triethylamine (Scheme 14) [111].
These products 34a–d were relatively unstable to air. Therefore, they were used in the following reactions immediately after their preparation.
The reaction of aryl-substituted isoselenocyanates 34a–c with allyl mercaptan afforded S-allyl-selenothiocarbamates 35a–c, which were involved in the reaction of intramolecular iodocyclization. The latter reaction led to 2-imino-1,3-thiaselenolanes 36a–c in up to 90% yields in the form of the Z/E-isomeric mixture in the imine position. The Z/E-isomerization of chalcogen-containing heterocycles bearing an exocyclic imine depends on both ring size and the nature of heteroatom in selenocarbonyl intermediates. In this case, the Z-isomer is predominantly formed (Scheme 14) [112].
Further structural modification of compounds 36a,b using diazabicycloundecene (DBU) as a dehydrohalogenating reagent [110] in dichloromethane at room temperature for 4 h produced five-membered products with two exocyclic double bonds—4-methylidene-2-phenylimino-1,3-thiaselenolane (37a) in 80% yield with preservation of stereochemistry (Z/E = 85:15) and 4-methylidene-2-(4-methylphenylimino)-1,3-thiaselenolane (37b) (Z/E = 85:15) in 57% yield (Scheme 14) [112].
The acid cyclization of S-allyl-phenylseleno thiocarbamate 35a in a hydrogen chloride solution of diethyl ether and ethyl acetate afforded 4-methyl-2-phenylimino-1,3-thiaselenolane 38a as a mixture of Z- and E-isomers in imine positions in 50% yield (Scheme 14) [112].

2.3. Oxidized Derivatives of 1,3-Thiaselenolane and 1,3-Thiaselenole

A four-membered heterocycle, 2,4-bis(chloromethyl)-1,3-thiaselenetane-1,1-dione (39), and a five-membered heterocycle, 5-chloro-2-chloromethyl-1,3-thiaselenolane-1,1-dione (40), were obtained in 55% yield (a 5/3 diastereomer ratio) and in 45% yield (a 3/1 diastereomer ratio), respectively, by the reaction of selenium dichloride with divinyl sulfone in acetonitrile at room temperature (Scheme 15) [113,114,115].
A similar reaction of selenium dibromide with divinyl sulfone with high stereoselectivity leads to the formation of the corresponding 2,4-bis(bromomethyl)-1,3-thiaselenetane-1,1-dione (41) (a 20/1 diastereomer ratio) in 78% yield and 5-bromo-2-bromomethyl-1,3-thiaselenolane 1,1-dione (42) (a 9/1 diastereomer ratio) in 22% yield (Scheme 15) [113,114,115].
Upon the action of pyridine on compounds 40 and 42, heterocycles 43 and 44 were regioselectively obtained in 80% and 62% yields, respectively. The dehydrohalogenation reaction resulted in the formation of only products containing an exocyclic double bond (Scheme 15) [113,114,115], unlike the dehydrohalogenation reactions of similar compounds with non-oxidized sulfur in the ring (Scheme 1, Scheme 2 and Scheme 3) [63,64,65,66,69,70,71,72]. In this case, the electron-withdrawing sulfonyl group increased the acidity of α-CH protons, and dehydrohalogenation, leading to an exocyclic double bond, became more preferable (Scheme 15) [113,114,115].
Triethylamine is a suitable reagent for generating carbon nucleophiles, which in turn can react with electrophilic centers [116]. The reaction of o-substituted 2-(bromoselanyl)benzenesulfonyl chloride (45) with a carbon nucleophile, which was obtained in situ from the active methylene group of 1,3-cyclohexadienone in the presence of triethylamine in methylene chloride, led to the formation of 2′H,6′H-spiro [1,3-benzothiaselenole-2,1′-cyclohexane]-2′,6′-dione 1,1-dioxide (46) in 60% yield (Scheme 16) [117].

2.4. 1,4,5,8-Diselenadithiafulvalene Derivatives

Derivatives of diselenadithiafulvalene are useful building blocks for organic synthesis and donor units for the preparation of charge-transfer complexes and radical ion salts, and the construction of organic metals, semiconductors, superconductors, ferromagnets and other conductive materials [36,37,38,39,40,41,42,43,44,45,46,47].
Four hybrid diselenadithiafulvalenes 47a–d conjugated with five-membered heterocycles that form highly conductive molecular complexes with 7,7,8,8-tetracyanoquinodimethane (TCNQ) were synthesized as new electron donors.
At the initial stage, derivatives of 1,3-dichalcogenole-2-chalcogenone 48a–d were formed by a cyclization reaction of commercially available tetrahydropyranyl-protected 3-butin-1-ol with chalcogen and carbon dichalcogenide in up to 95% yields.
Triethyl and trimethyl phosphite are known to catalyze cross-coupling reactions of ketones, thions, and selenones, giving composite fulvalene molecules [118,119,120,121,122]. The system of internal fulvalene rings—compounds 49a–d was formed in up to 86% yields by usual trimethyl phosphite-catalyzed coupling in the benzene solution. After removing the THP-protective group (compounds 50a–d, in yields up to 99%) and replacing the proton with a tosyl group (compounds 51a–d, in yields up to 98%), the outer heterocyclic rings were constructed at the last stage with the formation of diselenadithiafulvalenes 47a–d in up to 91% yields as a result of the transalkylation reaction of the chalcogen atom (Scheme 17) [123].
An effective synthetic method for the preparation of bis(ethylenedithio)diselenadithiafulvalene (52a) was developed. The reaction of 2-iodoethyltetrahydropyranyl ether (53) with potassium thiocyanate gave the corresponding thiocyanate 54 (yield 85%), which then reacted with ethynylmagnesium chloride, resulting in the formation of THP-protected 2-(ethynylthio)ethanol (55) in 54% yield. The lithium acetylide obtained from compound 55 with n-BuLi in the presence of tetramethylethylenediamine (TMEDA) was sequentially reacted with selenium, carbon disulfide and, finally, ethylthiocyanate to obtain thione 56a in 98% yield. The main intermediate 56a was converted to ketone 57, which was subjected to a self-coupling reaction in boiling trimethyl phosphite. The asymmetric diselenadithiafulvalene 58a was obtained in 91% yield as a mixture of conformational isomers (cis/trans) that was formed due to rotation around the central double bond. The intermediate compound 58a was successively treated with aqueous hydrochloric acid, tosyl chloride, and sodium iodide with the closure of the outer rings due to the transalkylation reaction of sulfur atoms and the formation of the expected product 52a in 82% yield (Scheme 18) [124].
Similarly, bis(ethyleneselenothio)diselenadithiafulvalenes 52b,c were obtained using the trimethyl phosphite-catalyzed homo-coupling of the corresponding thions and selenones, bypassing the stage of conversion to ketone (Scheme 19) [124].
The last two stages of this synthesis include treating intermediate products 56b,c with tosyl chloride in the presence of triethylamine, followed by sodium iodide-catalyzed cyclisation in DMF (Scheme 19) [124].
An evaluation of the half-wave oxidation potentials showed that the diselenadithiafulvalenes 52a–c obtained in this way have strong electron-donating properties [124].
For example, gallium- and copper-containing conducting salts κ-(cis-52a)2GaCl4, κ-(cis-52a)2Cu1.6Cl2.9 и λ’-(trans-52a)2GaCl4 were obtained for compound 52a [125].
Triselenathiafulvalene (61) was synthesized as a result of the homo-coupling of 4,5-dicarbomemethoxy-1,3-diselenole-2-thione 62 in the presence of triethyl phosphite and further decarbomethoxylation of compound 63 (yield 40%) (Scheme 20) [126]. This method is very promising because the initial semi-product 62 was obtained without the use of toxic carbon diselenide via intermediate titanocene pentaselenide 64 in 43% yield. At the cross-coupling stage, an inversion of an exocyclic sulfur atom and an endocyclic selenium atom occurs in one of the diselenole rings, resulting in the formation of a mixed thiaselenafulvene core. The final product, 61, containing three selenium atoms and one sulfur atom, was obtained in 37% yield (Scheme 20) [126].
The charge-transfer complex of triselenathiafulvalene 61 with tetracyanoquinodimethane demonstrated a high anisotropic conductivity in the polycrystalline sample, which decreased with increasing temperature (Scheme 20) [126].
It is also interesting is the reaction of sulfur–selenium exchange, in which one selenium atom in the molecular skeleton was replaced by an external sulfur atom. Ethylenedioxydithiadiselenafulvalene (65) was treated with lithium diisopropylamide (LDA) in dry tetrahydrofuran at −78 °C, followed by the addition of sulfur, and then zinc dichloride and tetrabutylammonium bromide at room temperature (Scheme 21) [127]. On the other hand, zinc dichloride and tetrabutylammonium bromide were added after the reaction of dithiadiselenafulvalene (66) with NaOMe in tetrahydrofuran/methanol solution at room temperature. The corresponding complex zinc salts 67 and 68 were precipitated. The reaction of these salts with 2-methylthio-1,3-dithiolylium tetrafluoroborate (69) in dimethylformamide led to the formation of ethylenedioxy- 70a2− (X = O) and ethylenedithiodithiadiselenafulvalenedithiolates 70b2− (X = S). The latter compounds were converted to the corresponding isomers 71a2− and 71b2− due to the selenium–sulfur exchange reaction, and thioquinone-1,3-dithiolemethides 72a and 72b were obtained as black solids in 30% and 15% total yields, respectively (Scheme 21) [127].
Compounds 72a and 72b are new perspective donor molecules for the preparation of conducting materials (Scheme 21) [127].
After electrochemical oxidation at a constant current of 0.2 µA in PhCl/EtOH solvent mixture (V/V = 9:1) containing a supporting electrolyte n-Bu4N∙FeCl4 or n-Bu4N∙FeBr4, at 35–45 °C, black single crystals with the composition 72a∙FeCl4 and 72b∙FeBr4 were grown on the surface of the platinum electrode [127,128]. These materials can be used as semiconductors.

3. Conclusions

An analysis of the literature data has shown that there has been a significant increase in interest in the chemistry of heterocycles containing both sulfur and selenium heteroatoms in the ring.
This review covers design and synthetic methods used for the preparation of 1,3-thiaselenolane and 1,3-thiaselenole derivatives over the last 20 years, with an emphasis on catalytic reactions. This class of compounds is relatively few in number, but very important. 1,3-Thiaselenolane and 1,3-thiaselenole derivatives include not only biologically active compounds, but also various conducting materials based on 1,4,5,8-diselenadithiafulvalenes.
Noteworthy is the efficient one-pot synthesis of 2-bromomethyl-1,3-thiaselenole (5) and its use in organic synthesis [63,64,65,66,69,70,71,72,75,76,77,78,79,87,88]. 2-Bromomethyl-1,3-thiaselenole (5) is a unique reagent that exhibits unusual properties in nucleophilic substitution reactions. The bromine atom in this reagent is highly activated by the strong anchimeric assistance effect of the selenium atom [74]. The chemical properties of this reagent show that it exists in equilibrium with corresponding seleniranium cation, and this is confirmed by quantum chemical calculations [79].
It can be concluded that the chemistry of the 1,3-thiaselenolane and 1,3-thiaselenole derivatives has great potential for successful development. This direction in organoselenium chemistry will be further enriched by new synthetic methods and valuable intermediates for organic synthesis and excellent electron donors for the preparation of conducting materials.

Author Contributions

Conceptualization and methodology, S.V.A.; writing—original draft preparation and writing—review and editing, N.A.M. 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.

Conflicts of Interest

The authors declare no conflict of interest.

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Catalysts 13 01221 sch001
Scheme 1. Reaction of selenium dichloride with divinyl sulfide.
Scheme 1. Reaction of selenium dichloride with divinyl sulfide.
Catalysts 13 01221 sch001
Catalysts 13 01221 sch002
Scheme 2. Reaction of selenium dibromide with divinyl sulfide in chloroform.
Scheme 2. Reaction of selenium dibromide with divinyl sulfide in chloroform.
Catalysts 13 01221 sch002
Catalysts 13 01221 sch003
Scheme 3. Reaction of selenium dibromide with divinyl sulfide in carbon tetrachloride.
Scheme 3. Reaction of selenium dibromide with divinyl sulfide in carbon tetrachloride.
Catalysts 13 01221 sch003
Catalysts 13 01221 sch004
Scheme 4. Possible formation of reaction products starting from thiaselenole 5 via seleniranium or thiiranium cations.
Scheme 4. Possible formation of reaction products starting from thiaselenole 5 via seleniranium or thiiranium cations.
Catalysts 13 01221 sch004
Catalysts 13 01221 sch005
Scheme 5. Reaction of 2-bromomethyl-1,3-thiaselenole (5) with ammonium thiocyanate and potassium selenocyanate in acetonitrile.
Scheme 5. Reaction of 2-bromomethyl-1,3-thiaselenole (5) with ammonium thiocyanate and potassium selenocyanate in acetonitrile.
Catalysts 13 01221 sch005
Catalysts 13 01221 sch006
Scheme 6. Synthesis of 1,3-thiaselenol-2-ylmethyl selenides 12a–l.
Scheme 6. Synthesis of 1,3-thiaselenol-2-ylmethyl selenides 12a–l.
Catalysts 13 01221 sch006
Catalysts 13 01221 sch007
Scheme 7. Synthesis of alkyl 3-[(1,3-thiaselenol-2-ylmethyl)selanyl]-2-propenoates 13a,b.
Scheme 7. Synthesis of alkyl 3-[(1,3-thiaselenol-2-ylmethyl)selanyl]-2-propenoates 13a,b.
Catalysts 13 01221 sch007
Catalysts 13 01221 sch008
Scheme 8. Reaction of 2-bromomethyl-1,3-thiaselenole (5) with mercapto benzazoles 14a–d.
Scheme 8. Reaction of 2-bromomethyl-1,3-thiaselenole (5) with mercapto benzazoles 14a–d.
Catalysts 13 01221 sch008
Catalysts 13 01221 sch009
Scheme 9. Reaction of 2-bromomethyl-1,3-thiaselenole (5) with 1-methyl-1H-imidazol-2-thiol (17).
Scheme 9. Reaction of 2-bromomethyl-1,3-thiaselenole (5) with 1-methyl-1H-imidazol-2-thiol (17).
Catalysts 13 01221 sch009
Catalysts 13 01221 sch010
Scheme 10. Reaction mechanism of 2-bromomethyl-1,3-thiaselenole (5) with 1-methyl-1H-imidazol-2-thiol (17).
Scheme 10. Reaction mechanism of 2-bromomethyl-1,3-thiaselenole (5) with 1-methyl-1H-imidazol-2-thiol (17).
Catalysts 13 01221 sch010
Catalysts 13 01221 sch011
Scheme 11. Synthesis of 2-methyl-5-{[(1,3-thiaselenol-2-yl)methyl]sulfanyl}-1,3,4-thiadiazole (24).
Scheme 11. Synthesis of 2-methyl-5-{[(1,3-thiaselenol-2-yl)methyl]sulfanyl}-1,3,4-thiadiazole (24).
Catalysts 13 01221 sch011
Catalysts 13 01221 sch012
Scheme 12. Synthesis of 1,3-thiaselenolane 30.
Scheme 12. Synthesis of 1,3-thiaselenolane 30.
Catalysts 13 01221 sch012
Catalysts 13 01221 sch013
Scheme 13. Synthesis of functionalized 1,3-thiaselenolanes 33a,b.
Scheme 13. Synthesis of functionalized 1,3-thiaselenolanes 33a,b.
Catalysts 13 01221 sch013
Catalysts 13 01221 sch014
Scheme 14. Synthesis of 2-imino-1,3-thiaselenolanes 36a–c and its derivatives 37a,b and 38a.
Scheme 14. Synthesis of 2-imino-1,3-thiaselenolanes 36a–c and its derivatives 37a,b and 38a.
Catalysts 13 01221 sch014
Catalysts 13 01221 sch015
Scheme 15. Reaction of selenium dichloride and dibromide with divinyl sulfone.
Scheme 15. Reaction of selenium dichloride and dibromide with divinyl sulfone.
Catalysts 13 01221 sch015
Catalysts 13 01221 sch016
Scheme 16. Synthesis of 2′H,6′H-spiro [1,3-benzothiaselenole-2,1′-cyclohexane]-2′,6′-dione 1,1-dioxide (46).
Scheme 16. Synthesis of 2′H,6′H-spiro [1,3-benzothiaselenole-2,1′-cyclohexane]-2′,6′-dione 1,1-dioxide (46).
Catalysts 13 01221 sch016
Catalysts 13 01221 sch017
Scheme 17. Synthesis of diselenadithiafulvalenes 47a–d.
Scheme 17. Synthesis of diselenadithiafulvalenes 47a–d.
Catalysts 13 01221 sch017
Catalysts 13 01221 sch018
Scheme 18. Synthesis of bis(ethylenedithio)diselenadithiafulvalene (52a).
Scheme 18. Synthesis of bis(ethylenedithio)diselenadithiafulvalene (52a).
Catalysts 13 01221 sch018
Catalysts 13 01221 sch019
Scheme 19. Synthesis of bis(ethyleneselenothio)diselenadithiafulvalenes (52b,c).
Scheme 19. Synthesis of bis(ethyleneselenothio)diselenadithiafulvalenes (52b,c).
Catalysts 13 01221 sch019
Catalysts 13 01221 sch020
Scheme 20. Synthesis of triselenathiafulvalene (61).
Scheme 20. Synthesis of triselenathiafulvalene (61).
Catalysts 13 01221 sch020
Catalysts 13 01221 sch021
Scheme 21. Synthesis of thioquinone-1,3-dithiolemethides 72a and 72b.
Scheme 21. Synthesis of thioquinone-1,3-dithiolemethides 72a and 72b.
Catalysts 13 01221 sch021
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Amosova, S.V.; Makhaeva, N.A. Recent Advances in Design and Synthesis of 1,3-Thiaselenolane and 1,3-Thiaselenole Derivatives. Catalysts 2023, 13, 1221. https://doi.org/10.3390/catal13081221

AMA Style

Amosova SV, Makhaeva NA. Recent Advances in Design and Synthesis of 1,3-Thiaselenolane and 1,3-Thiaselenole Derivatives. Catalysts. 2023; 13(8):1221. https://doi.org/10.3390/catal13081221

Chicago/Turabian Style

Amosova, Svetlana V., and Nataliya A. Makhaeva. 2023. "Recent Advances in Design and Synthesis of 1,3-Thiaselenolane and 1,3-Thiaselenole Derivatives" Catalysts 13, no. 8: 1221. https://doi.org/10.3390/catal13081221

APA Style

Amosova, S. V., & Makhaeva, N. A. (2023). Recent Advances in Design and Synthesis of 1,3-Thiaselenolane and 1,3-Thiaselenole Derivatives. Catalysts, 13(8), 1221. https://doi.org/10.3390/catal13081221

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