Click Chemistry of Selenium Dihalides: Novel Bicyclic Organoselenium Compounds Based on Selenenylation/Bis-Functionalization Reactions and Evaluation of Glutathione Peroxidase-like Activity

Abstract

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.

First Examples of Reactions of 3-Trimethylsilyl-2-Propynamides and Organic Diselenides: Synthesis of Novel Derivatives of Propynamides

“…Recently, we developed the synthesis of 2,6-bis(1,2,3-triazol-1-yl)-9-selenabicyclo[3.3.1] nonanes through the copper-catalyzed azide-alkynes 1,3-dipolar cycloaddition reaction [47,48]. The Cu(OAc) 2 /sodium ascorbate catalytic system was used to carry out the cycloaddition reaction.…”

“…The target products 13a,b were also obtained in this case, but in lower yield (about 50%), and the reaction proceeded less selectively. Recently, we developed the synthesis of 2,6-bis(1,2,3-triazol-1-yl)selenabicyclo[3.3.1]nonanes through the copper-catalyzed azide-alkynes 1,3-dipolar cy cloaddition reaction [47,48]. The Cu(OAc)2/sodium ascorbate catalytic system was use to carry out the cycloaddition reaction.…”

Polyunsaturated sulfur/selenium-containing products based on regio- and stereoselective nucleophilic addition and substitution reactions of 1,2-bis[(Z)-2-(vinylsulfanyl)ethenyl] diselane

“…9 Organoselenium compounds exhibit glutathione peroxidase-like properties and can be used to treat diseases associated with oxidative stress, such as ischemic stroke, cardiovascular, Alzheimer's and Parkinson's disease. 10–13…”

“…9 Organoselenium compounds exhibit glutathione peroxidase-like properties and can be used to treat diseases associated with oxidative stress, such as ischemic stroke, cardiovascular, Alzheimer's and Parkinson's disease. [10][11][12][13] Ebselen is the best-known organoselenium synthetic drug that mimics the catalytic activity of glutathione peroxidase. [14][15][16][17] Ebselen acts as a catalyst in converting hydrogen peroxide to harmless water molecules.…”

“…CF = 8.0 Hz, C-2,6), 160.60 ( 1 J CF = 245.9 Hz, C-4); 19 F (376 MHz, CDCl 3 ): d = À114.91 ( 3 J FH(3,5) = 8.7 Hz, 4 J FH(2,6) = 5.4 Hz); 77 Se (76 MHz, CDCl 3 ): d = 327.75, 327.79 ( 6 J FSe = 3.7 Hz); EI-MS m/z (%): 274 (9, M + ), 165 (3), 151(25), 109 (100), 83(18), 59(10), 58 (8); anal. calcd for C 11 H 11 FSSe: C, 48.35; H, 4.06.…”