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13 pages, 2796 KB

Open AccessArticle

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

Catalysts 2023, 13(8), 1227; https://doi.org/10.3390/catal13081227 - 21 Aug 2023

Cited by 2 | Viewed by 1760

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. Full article

(This article belongs to the Special Issue Recent Advances in Catalytic Synthesis and Application of Heterocyclic and Heteroatom Compounds)

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20 pages, 4342 KB

Open AccessReview

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

by Svetlana V. Amosova and Nataliya A. Makhaeva

Catalysts 2023, 13(8), 1221; https://doi.org/10.3390/catal13081221 - 17 Aug 2023

Cited by 2 | Viewed by 2489

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. Full article

(This article belongs to the Special Issue Recent Advances in Catalytic Synthesis and Application of Heterocyclic and Heteroatom Compounds)

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18 pages, 5046 KB

Open AccessArticle

Green Organoselenium Chemistry: Selective Syntheses of New 1,4-Thiaselenine Derivatives Based on Reactions of Thiaselenole Reagent with Alcohols and Water

by Svetlana V. Amosova, Andrey S. Filippov, Nataliya A. Makhaeva, Alexander I. Albanov and Vladimir A. Potapov

Inorganics 2023, 11(7), 281; https://doi.org/10.3390/inorganics11070281 - 29 Jun 2023

Cited by 3 | Viewed by 1584

Abstract

Environmentally friendly synthetic methods were developed for the selective preparation of new 2,3-dihydro-1,4-thiaselenine derivatives in high yields based on the reactions of 2-bromomethyl-1,3-thiaselenole with alcohols and water at room temperature. The reaction of 2-bromomethyl-1,3-thiaselenole with alcohols was accompanied by a rearrangement with ring extension, leading to six-membered heterocyclic compounds, a new family of 2-organyloxy-2,3-dihydro-1,4-thiaselenines, in 80–96% yields. The remarkable cascade reactions of 2-bromomethyl-1,3-thiaselenole with water afforded 2,3-dihydro-1,4-thiaselenines functionalized with the (Z)-S-CH=CH-Se fragment and one or two highly reactive aldehyde groups. The latter aldehydes were functionalized by the reactions with alcohols and glycols to give new polyfunctionalized compounds, containing two double bonds, two sulfur atoms, two selenium atoms, and two or four oxygen atoms, in high yields. Full article

(This article belongs to the Special Issue Selective Synthesis of New Organometallic and Organochalcogen Compounds Based on Inorganic Reagents)

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14 pages, 1448 KB

Open AccessFeature PaperArticle

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

Catalysts 2022, 12(10), 1236; https://doi.org/10.3390/catal12101236 - 14 Oct 2022

Cited by 3 | Viewed by 2699

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. Full article

(This article belongs to the Special Issue The Influence of Phase Transfer Catalysis (PTC) in the Synthesis of Bioactive Compounds)

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15 pages, 2730 KB

Open AccessArticle

Regioselective Synthesis of Novel Functionalized Dihydro-1,4-thiaselenin-2-ylsufanyl Derivatives under Phase Transfer Catalysis

by Andrey S. Filippov, Svetlana V. Amosova, Alexander I. Albanov and Vladimir A. Potapov

Catalysts 2022, 12(8), 889; https://doi.org/10.3390/catal12080889 - 12 Aug 2022

Cited by 3 | Viewed by 2131

Abstract

The regioselective one-pot synthesis of novel functionalized 2,3-dihydro-1,4-thiaselenin-2-ylsufanyl derivatives in high yields based on 2-bromomethyl-1,3-thiaselenole and activated alkenes was developed under phase transfer catalysis conditions. The reactions proceed under mild conditions at room temperature in a regioselective manner with the addition of sodium dihydro-1,4-thiaselenin-2-ylthiolate exclusively at the terminal carbon atom of the double bond of vinyl methyl ketone, alkylacrylates, acrylamide, acrylonitrile, divinyl sulfone, and divinyl sulfoxide. The sodium dihydro-1,4-thiaselenin-2-ylthiolate was generated from 2-[amino(imino)methyl]sulfanyl-2,3-dihydro-1,4-thiaselenine hydrobromide. The latter compound was obtained by the reaction of 2-bromomethyl-1,3-thiaselenole with thiourea, which was accompanied by a rearrangement with ring expansion to the six-membered heterocycle. The obtained 2,3-dihydro-1,4-thiaselenin-2-ylsufanyl derivatives are a novel family of compounds with putative biological activity. The addition products of sodium dihydro-1,4-thiaselenin-2-ylthiolate at one double bond of divinyl sulfone and divinyl sulfoxide, containing vinylsulfonyl and vinylsulfinyl groups, are capable of further addition reactions. A possibility to obtain corresponding alcohol derivatives was shown in the reaction with vinyl methyl ketone. Full article

(This article belongs to the Special Issue The Influence of Phase Transfer Catalysis (PTC) in the Synthesis of Bioactive Compounds)

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16 pages, 3895 KB

Open AccessArticle

Quantum Chemical and Experimental Studies of an Unprecedented Reaction Pathway of Nucleophilic Substitution of 2-Bromomethyl-1,3-thiaselenole with 1,3-Benzothiazole-2-thiol Proceeding Stepwise at Three Different Centers of Seleniranium Intermediates

by Svetlana V. Amosova, Vladimir A. Shagun, Nataliya A. Makhaeva, Irina A. Novokshonova and Vladimir A. Potapov

Molecules 2021, 26(21), 6685; https://doi.org/10.3390/molecules26216685 - 4 Nov 2021

Cited by 9 | Viewed by 3776

Abstract

The results of quantum chemical and experimental studies of the reaction of 2-bromomethyl-1,3-thiaselenole with 1,3-benzothiazole-2-thiol made it possible to discover the unprecedented pathway of this reaction, which proceeds stepwise at three different centers of seleniranium intermediates. The first stage includes an attack of thiolate anion at the selenium atom of the seleniranium cation accompanied by ring opening with the formation of (Z)-2-[(1,3-benzothiazol-2-ylsulfanyl)selanyl]ethenyl vinyl sulfide, which is converted to six-membered heterocycle, 2-(2,3-dihydro-1,4-thiaselenin-2-ylsulfanyl)-1,3-benzothiazole, in a 99% yield. The latter compound undergoes rearrangement with ring contraction producing five-membered heterocycle, 2-[(1,3-thiaselenol-2-ylmethyl)sulfanyl]-1,3-benzothiazole, in a 99% yield (the thermodynamic product). The formation of 1,2-bis[(Z)-2-(vinylsulfanyl)ethenyl] diselenide is the result of the disproportionation of (Z)-2-[(1,3-benzothiazol-2-ylsulfanyl)selanyl]ethenyl vinyl sulfide. Thus, based on the quantum chemical and experimental studies, a regioselective synthesis of the reaction products in high yields was developed. Full article

(This article belongs to the Special Issue Novel Organic Heteroatom Compounds: Synthesis Design and Theoretical Studies)

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