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Highly efficient and convenient methods for the preparation of 35 novel derivatives of 9-selenabicyclo[3.3.1]nonane and 9-selenabicyclo[3.3.1]nonene-2 in high yields based on the adduct of the transannular addition of SeBr2 to 1,5-cyclooctadiene were developed. The methods for the amination of the adduct made it possible to obtain both diamino selenabicyclo[3.3.1]nonane derivatives and their dihydrobromide salts in one step in 88–98% yields. The methods meet the criteria of click chemistry. Compounds with high glutathione peroxidase mimetic activity were found among water-soluble dihydrobromide salts. The selective reaction of 2,6-dibromo-9-selenabicyclo[3.3.1]nonane with acetonitrile to form 6-bromo-9-selenabicyclo[3.3.1]nonene-2 was discovered. The latter compound served as a promising starting material to give rise to the new class of selenabicyclo[3.3.1]nonene-2 derivatives, e.g., 6-alkoxy-9-selenabicyclo[3.3.1]nonenes were obtained in 94–99% yields. [ABSTRACT FROM AUTHOR]

The last decade has witnessed significant progress in the development of novel synthetic methods for the preparation of a variety of new functionalized and condensed compounds via reactions of organic dichalcogenides with acetylenic derivatives. The present review highlights recent developments in the synthesis of organoselenium compounds based on the reactions of organic diselenides with acetylenes over the past few years. The discussion mainly focuses on the literature data for the last 5 years. It is worth noting that the lion's share of this material is devoted to catalytic and electrophile-mediated reactions with aromatic compounds, containing a triple bond and nucleophilic functional groups. [ABSTRACT FROM AUTHOR]

Oxidative stress is the cause of various pathologies and disorders of cellular functions. Substances that reduce the pathological effect of oxidative stress on homeostasis include organoselenium compounds of natural and synthetic origin. Depending on the structure, organoselenium compounds can exhibit different biological activities, for example, reducing oxidative stress, participating in the regulation of signaling systems, influencing the synthesis of cytokines, etc. This makes them promising products for the development of new means of metabolic correction and drugs with enzyme-like activity. This study is aimed at developing an effective method for the synthesis of functional organoselenium compounds and studying their antioxidant effect in vivo under stress conditions. A one-pot catalyst-free method of transannular addition-functionalization of cis,cis-1,5-cyclooctadiene with selenium dihalides in the presence of nucleophiles was developed. For the first time, the antioxidant activity of functionalized 9-selenabicyclo[3.3.1]nonanes was studied in vivo. Quantitative characteristics of the effect on the level of lipid peroxidation and the activity of glutathione peroxidase and glutathione reductase under stress conditions were obtained. The effect of substituents in the selenium-containing scaffold on the biological activity of the compounds was studied. The water-soluble 9-selenabicyclo[3.3.1]nonane derivatives, containing hydroxyl and 2-hydroxyethoxy groups, which increased the activity of both glutathione peroxidase and glutathione reductase, were discovered. [ABSTRACT FROM AUTHOR]

A number of highly efficient methods for the preparation of novel derivatives of 9-selenabicyclo[3.3.1]nonane in high yields based on selenium dibromide and cis,cis-1,5-cyclooctadiene are reported. The one-pot syntheses of 2,6-diorganyloxy-9-selenabicyclo[3.3.1]nonanes using various O-nucleophiles including alkanols, phenols, benzyl, allyl, and propargyl alcohols were developed. New 2,6-bis(1,2,3-triazol-1-yl)-9-selenabicyclo[3.3.1]nonanes were obtained by the copper-catalyzed 1,3-dipolar cycloaddition of 2,6-diazido-9-selenabicyclo[3.3.1]nonane with unsubstituted gaseous acetylene and propargyl alcohol. The synthesis of 2,6-bis(vinylsulfanyl)-9-selenabicyclo[3.3.1]nonane, based on the generation of corresponding dithiolate anion from bis[amino(iminio)methylsulfanyl]-9-selenabicyclo[3.3.1]nonane dibromide, followed by the nucleophilic addition of the dithiolate anion to unsubstituted acetylene, was developed. The glutathione peroxidase-like activity of the obtained water-soluble products was estimated and compounds with high activity were found. Overall, 2,6-Diazido-9-selenabicyclo[3.3.1]nonane exhibits the highest activity among the obtained compounds. [ABSTRACT FROM AUTHOR]

The one-pot efficient synthesis of novel functionalized organoselenium compound by bis-alkoxyselenenylation of alkenes with selenium dibromide and alcohols was developed. The reaction of the selenium dibromide with cyclopentene or cyclohexene in the system alcohol/sodium bicarbonate/methylene chloride at room temperature afforded bis(2-alkoxycycloalkyl) selenides in 90–99% yields. The regioselective and efficient method for bis-alkoxylation of terminal alkenes was developed based on the addition of selenium dibromide with 1-alkenes in acetonitrile followed by refluxing of addition products in alcohols in the presence of traces of sulfuric acid. This method made it possible to selectively obtain bis(2-alkoxyalkyl) selenides in 94–98% yields. [ABSTRACT FROM AUTHOR]

The catalytic regioselective and highly efficient synthesis of bis-1,2,3-triazole derivatives of 9-selenabicyclo[3.3.1]nonane was developed. The 1,3-dipolar cycloaddition reaction of 2,6-diazido-9-selenabicyclo[3.3.1]nonane with a variety of terminal acetylenes catalyzed by a copper acetate/sodium ascorbate system proceeded in a regioselective fashion, affording 2,6-bis(4-organyl-1,2,3-triazole)-9-selenabicyclo[3.3.1]nonanes in high yields (93–98%). The reaction of 2,6-diazido-9-selenabicyclo[3.3.1]nonane with dimethyl and diethyl acetylenedicarboxylates was carried out as thermal 1,3-dipolar Huisgen cycloaddition giving the corresponding 4,5-disubstituted 1,2,3-triazole derivatives of 9-selenabicyclo[3.3.1]nonane in high yields. The obtained products are potentially bioactive compounds and first representatives of selenium heterocycles combined with two 1,2,3-triazole moieties. 2.6-Diazido-9-selenabicyclo[3.3.1]nonane was obtained in quantitative yield via the reaction of sodium azide with 2,6-dibromo-9-selenabicyclo[3.3.1]nonane at room temperature. The latter compound was synthesized by stereoselective transannular addition of selenium dibromide to cis, cis-1,5-cyclooctadiene. [ABSTRACT FROM AUTHOR]

A novel methodology to accelerate annulation reactions leading to condensed selenium heterocycles was developed. The reactions of selenium dihalides with methyleugenol, allyl thymyl ether, allyl 1-naphthyl and 1-naphthyl propargyl ethers were carried out in the presence of alcohols, which considerably accelerated the annulation reactions. In solvent systems CH2Cl2/MeOH or CHCl3/MeOH, the reactions proceeded as annulation–methoxylation affording condensed methoxylated heterocycles. In the presence of isopropanol, the reactions were not accompanied by alkoxylation giving condensed halogen-containing products. The annulation reaction of selenium dihalides with 1-naphthyl propargyl ether included stereoselective anti-addition to the triple bond. The efficient selective synthesis of the first representatives of novel families of condensed selenium heterocycles with promising biological activity was developed. [ABSTRACT FROM AUTHOR]

The reactions of selenium dihalides, tellurium tetrachloride and tetrabromide with 3-hexyne and 4-octyne proceed in a stereoselective manner as anti-addition to afford products of E-stereochemistry. First examples of bis-adduct synthesis from tellurium tetrachloride and disubstituted acetylenes as well as of the addition of tellurium tetrabromide to disubstituted acetylenes were described. Reaction conditions for efficient stereoselective synthesis of E-2-halovinyl tellanes, ditellanes and selenides were developed. [ABSTRACT FROM AUTHOR]

First examples of the reactions of 3-trimethylsilyl-2-propynamides with organic diselenides yielding 3-alkylselanyl-2-propenamides and 3-organylselanyl-2-propynamides were realized. The latter compounds were obtained by the Cu-catalyzed reaction of organic diselenides with 4-propioloylmorpholine. The reaction of 3-trimethylsilyl-2-propynamides with dialkyl diselenides in the system NaBH4/H2O/K2CO3/THF proceeded in a regio- and stereoselective fashion, affording 3-alkylselanyl-2-propenamides in 90–94% yields. An unsymmetrical divinyl selenide with the cyclic amide groups and a product, containing two selanyl-2-propenamide moieties and three cyclic amide groups, were synthesized. The Cu-catalyzed allylation reaction of 3-trimethylsilyl-2-propynamides was accompanied with desilylation to yield 3-allyl-2-propynamides. [ABSTRACT FROM AUTHOR]

An efficient approach to a novel family of (Z)-3-amino-3-oxo-1-propenyl selenocyanates was developed based on the reaction of KSeCN with 3-trimethylsilyl-2-propynamides in the presence of ammonium chloride in methanol. The reaction was accompanied by a desilylation process. The products were not formed under the same reaction conditions in the absence of ammonium chloride, which was used for the first time in the reactions of selenocyanates with acetylenes. The use of this new methodology allowed the reaction to carry out in a regio- and stereoselective fashion as anti-addition affording vinyl selenocyanates with a (Z)-configuration in high yields. [ABSTRACT FROM AUTHOR]

Highly efficient stereoselective syntheses of novel bis(E-2-chlorovinyl) selenides and bis(E-2-bromovinyl) selenides in quantitative yields by reactions of selenium dichloride and dibromide with alkynes were developed. The reactions proceeded at room temperature as anti-addition giving products exclusively with (E)-stereochemistry. The glutathione peroxidase-like activity of the obtained products was estimated and compounds with high activity were found. The influence of substituents in the products on their glutathione peroxidase-like activity was discussed. [ABSTRACT FROM AUTHOR]

Abstract: Efficient stereoselective synthesis of (E,E)-bis(2-chlorovinyl) and (E,E)-bis(2-bromovinyl) selenides in 95–98% yield based on the reactions of selenium dihalides or monohalides with acetylene has been elaborated. Reactions of selenium tetrahalides with acetylene afford (E,E)-bis(2-halovinyl) selenides and (E)-2-halovinyl 1,2,2-trihaloethyl selenides. Convenient synthesis of (E,E)-bis(2-halovinyl) selenium dihalides in near quantitative yield has been developed. (E,E)-Bis(2-halovinyl) selenium dihalides undergo spontaneous rearrangement with the halogen migration from the selenium atom to the double bond. The previously described reactions of selenium monochloride and tetrabromide with acetylene have been reinvestigated. [Copyright &y& Elsevier]

The Pd/Cu-catalyzed Sonogashira reaction of (E,E)-bis(2-bromovinyl) selenide and (E,E)-bis(1-bromo-1-hexen-2-yl) selenide with terminal alkynes was found to proceed at room temperature involving both bromine atoms and the selanyl function. As a result, new bis-(1,3-enynyl) selenides and enediyne hydrocarbons are formed with a complete retention of the stereoconfiguration of the initial selenides. Due to steric hindrances in the cross-coupling at the selenyl function in the case of (E,E)-bis(1-bromo-1-hexen-2-yl) selenide, the second process is realized to a lesser extent than with unsubstituted (E,E)-bis(2-bromovinyl) selenide. [ABSTRACT FROM AUTHOR]

Abstract: Highly chemo-, regio-, and stereoselective syntheses of novel organoselenium compounds from selenium dichloride or dibromide and unsaturated ethers are described. The reactions of selenium dichloride with allyl and propargyl phenyl ethers afford either annulated products or bis-adducts depending on the conditions. The first examples of annulation of 3-chloromethyl- and 3-chloromethylene-2,3-dihydro-1,4-oxaselenine to the benzene ring are reported. [Copyright &y& Elsevier]

The regioselective synthesis of novel functionalized condensed organochalcogen compounds by chalcogenocyclofunctionalization reactions based on chalcogen halides and the natural products thymol and carvacrol has been developed. The reactions of selenium dibromide with allyl thymol and allyl carvacrol proceeded in methylene chloride at room temperature in the presence of NaHCO3 affording bis[(7-isopropyl-4-methyl-2,3-dihydro-1-benzofuran-2-yl)methyl] and bis[(4-isopropyl-7-methyl-2,3-dihydro-1-benzofuran-2-yl)methyl] selenides in 90–92% yield. Similar sulfides were obtained in 70–72% yields by the reaction of sulfur dichloride in chloroform under reflux. Trihalotellanes containing the same organic moieties were synthesized from allyl thymol, allyl carvacrol and tellurium tetrachloride or tetrabromide in quantitative yields. Corresponding functionalized ditellurides were prepared in 91–92% yields by the reduction of the trichlorotellanes with sodium metabisulfite in two-phase solvent system. The comparison of reactivity of sulfur, selenium and tellurium halides in chalcogenocyclofunctionalization and distinguishing features of each reaction were discussed. [ABSTRACT FROM AUTHOR]

The efficient synthesis of a new family of 2,6-disulfanyl-9-selenabicyclo[3.3.1]nonanes in high yields has been developed based on 9-selenabicyclo[3.3.1]nonane-2,6-dithiolate anion generated from bis-isothiouronium salt of 2,6-dibromo-9-selenabicyclo[3.3.1]nonane. The derivatives of 2,6-disulfanyl-9-selenabicyclo[3.3.1]nonane containing alkyl, allyl and benzyl moieties have been prepared in 90–99% yields by nucleophilic substitution of 9-selenabicyclo[3.3.1]nonane-2,6-dithiolate anion with alkyl, allyl and benzyl halides. The reaction of nucleophilic addition of 9-selenabicyclo[3.3.1]nonane-2,6-dithiolate anion to alkyl propiolates afforded 2,6-di(vinylsulfanyl)-9-selenabicyclo[3.3.1]nonanes. The conditions for regio- and stereoselective addition of 9-selenabicyclo[3.3.1]nonane-2,6-dithiolate anion to a triple bond of alkyl propiolates have been found. To date, not a single representative of 2,6-disulfanyl-9-selenabicyclo[3.3.1]nonanes has been described in the literature. [ABSTRACT FROM AUTHOR]

The efficient regio- and stereoselective syntheses of (Z,Z)-bis(3-amino-3-oxo-1-propenyl) selenides and diselenides in high yields based on the nucleophilic addition of sodium selenide to 2-propynamides and sodium diselenide to 3-(trimethylsilyl)-2-propynamides have been developed. The first examples of the addition of a selenium-centered nucleophile to 2-propynamides with a terminal triple bond and diselenide anion to 3-(trimethylsilyl)-2-propynamides have been carried out. Bis(3-amino-3-oxo-1-propenyl) diselenides are a novel family of compounds, none of which has yet been described in the literature. The glutathione peroxidase-like activity of the obtained compounds has been evaluated and products with high activity have been found. It was established that diselenides are superior to selenides with the same substituents in glutathione peroxidase-like activity. The results of the structural studying of products by single-crystal X-ray diffraction analysis and 77Se-NMR data are discussed. [ABSTRACT FROM AUTHOR]

The original goal of this research was to study stereochemistry of selenium dihalides addition to cycloalkenes and properties of obtained products. Remarkable alkene-to-alkene and alkene-to-alkyne transfer reactions of selenium dibromide and PhSeBr were discovered during this research. The adducts of selenium dibromide with alkenes or cycloalkenes easily exchange SeBr2 with other unsaturated compounds, including acetylenes, at room temperature, in acetonitrile. Similar alkene-to-alkene and alkene-to-alkyne transfer reactions of the PhSeBr adducts with alkenes or cycloalkenes take place. The supposed reaction pathway includes the selenium group transfer from seleniranium species to alkenes or alkynes. It was found that the efficient SeBr2 and PhSeBr transfer reagents are Se(CH2CH2Br)2 and PhSeCH2CH2Br, which liberate ethylene, leading to a shift in equilibrium. The regioselective and stereoselective synthesis of bis(E-2-bromovinyl) selenides and unsymmetrical E-2-bromovinyl selenides was developed based on the SeBr2 and PhSeBr transfer reactions which proceeded with higher selectivity compared to analogous addition reactions of SeBr2 and PhSeBr to alkynes under the same conditions. [ABSTRACT FROM AUTHOR]

Review: 134 refs. [ABSTRACT FROM AUTHOR]

Abstract: The reactions of selenium dichloride and dibromide with divinyl sulfone leading to novel selenium heterocycles, 2,4-bis(halomethyl)-1,3-thiaselenetane-1,1-diones and 5-halo-2-halomethyl-1,3-thiaselenolane-1,1-diones, have been studied. Under the action of silica gel or pyridine, 5-halo-2-halomethyl-1,3-thiaselenolane-1,1-diones undergo facile regioselective dehydrohalogenation into 5-halo-2-methylene-1,3-thiaselenolane-1,1-diones. [Copyright &y& Elsevier]

The efficient regio- and stereoselective synthesis of (Z,Z)-3,3′-selanediylbis(2-propenamides) in 76–93% yields was developed based on the reaction of sodium selenide with 3-trimethylsilyl-2-propynamides. (Z,Z)-3,3′-Selanediylbis(2-propenamides) are a novel class of organoselenium compounds. To date, not a single representative of 3,3′-selanediylbis(2-propenamides) has been described in the literature. Studying glutathione peroxidase-like properties by a model reaction showed that the activity of the obtained products significantly varies depending on the organic moieties in the amide group. Divinyl selenide, which contains two lipophilic cyclohexyl substituents in the amide group, exhibits very high glutathione peroxidase-like activity and this compound is considerably superior to other products in this respect. [ABSTRACT FROM AUTHOR]

The transannular addition of SeCl2 and SeBr2 to cis,cis-cycloocta-1,5-diene affords 2,6-dihalo-9-selenabicyclo[3.3.1]nonanes in high yields. The latter react with SeCl2 and SeBr2 to form the 2 : 1 complexes, which are the first representatives of coordination compounds with the Se…Se…Se bonds. X-ray crystallographic data of the obtained compounds are discussed. In contrast to 2,6-dihalo-9-selenabicyclo[3.3.1]nonanes, tetrahydroselenophene does not form complexes with SeCl2 and SeBr2 giving 1,1-dihalotetrahydroselenophenes. [ABSTRACT FROM AUTHOR]

Regio- and stereoselective syntheses of novel unsaturated chalcogen-containing pyridine derivatives [3-(vinylsulfanyl)- and 3-(vinylselanyl)-2 H ,3 H -[1,3]thiazolo[3,2- a ]pyridin-4-ium chlorides, ethyl 3-(2-pyridinylsulfanyl)-2-propenoate, 1-phenyl-3-(2-pyridinylsulfanyl)-2-propen-1-one, allenyl 2-pyridinyl telluride] have been developed using the previously unknown electrophilic and nucleophilic reactions of 2-pyridinylsulfanyl chloride and 2-pyridinechalcogenolate anions. [ABSTRACT FROM AUTHOR]