Synthesis of a new four-membered heterocycle by reaction of selenium dichloride with divinyl sulfone

Abstract

SHORT COMMUNICATIONSSelenium dichloride and dibromide were not isolated as individual substances. It is known that selenium dichloride in solution exists in equilibrium with selenium tetrachloride and Se 2 Cl 2 , whereas the equilibrium of selenium dibromide in solution involves Se 2 Br 2 and bromine [1, 2]. We were the first to reveal that freshly prepared selenium dichloride and selenium dibromide can be used in selective synthesis of organic selenides [3,4]. Reactions of selenium dichloride and dibromide with divinyl chalcogenides and their derivatives opened a synthetic route to new heterocyclic compounds [5][6][7][8][9][10].In continuation of our systematic studies on the chemical properties of selenium dihalides [3-10], we examined previously unknown addition of selenium dichloride to divinyl sulfone. It was found that the reaction occurs with high regioselectivity and leads to the formation of a new four-membered heterocyclic compound, 2,4-bis(chloromethyl)-1,3-thiaselenetane 1,1-dioxide (I). The yield of compound I was 85%, calculated on the reacted divinyl sulfone, the conversion of the latter being 58%. sional correlation techniques, as well as by mass spectrometry and elemental analysis. According to the NMR data, compound I was isolated as a mixture of two diastereoisomers at a ratio of 2.5 : 1.2,4-Bis(chloromethyl)-1,3-thiaselenetane 1,1-dioxide (I). mp 76-77°C. Major diastereoisomer: 1 H NMR spectrum, δ, ppm: 3.91 d.d (2H, CH 2 Cl, 2 J = 11.8, 3 J = 7.1 Hz), 4.27 d.d (2H, CH 2 Cl, 2 J = 11.8, 3 J = 7.1 Hz), 5.52 d.d (2H, CHSe, 3 J = 7.1, 7.1 Hz). 13 C NMR spectrum, δ C , ppm: 41.39 (CH 2 Cl), 69.36 (CHSe). 77 Se NMR spectrum: δ Se 193 ppm. Minor diastereoisomer: 1 H NMR spectrum, δ, ppm: 3.93 d.d (2H, CH 2 Cl, 2 J = 11.9, 3 J = 7.7 Hz), 4.31 d.d (2H, CH 2 Cl, 2 J = 11.9, 3 J = 7.9 Hz), 5.54 d.d (2H, CHSe, 3 J = 7.7, 7.9 Hz). 13 C NMR spectrum, δ C , ppm: 41.63 (CH 2 Cl), 70.03 (CHSe). 77 Se NMR spectrum: δ Se 200 ppm. Mass spectrum, m/z (I rel , %): 268 (29)

Selenium Dihalides Click Chemistry: Highly Efficient Stereoselective Addition to Alkynes and Evaluation of Glutathione Peroxidase-Like Activity of Bis(E-2-halovinyl) Selenides

“…However, freshly prepared in situ from elemental selenium and sulfuryl chloride or bromine, these reagents can be successfully involved in further reactions [ 7 , 8 , 9 , 10 ]. Since then, the application of selenium dihalides in organic synthesis is intensively developing and makes it possible to obtain new classes of organoselenium compounds and selenium-containing heterocycles [ 13 , 14 , 15 , 16 , 17 , 18 , 19 , 20 , 21 , 22 , 23 , 24 , 25 , 26 ].…”

Efficient Synthesis of a New Family of 2,6-Disulfanyl-9-selenabicyclo[3.3.1]nonanes

“…The addition of selenium dihalides to alkenes and alkynes afforded bis(2-haloalkyl) selenides [ 45 , 46 ] and bis(2-halovinyl) selenides in high yields [ 47 , 48 , 49 , 50 , 51 , 52 ]. Novel heterocycles [ 53 , 54 , 55 , 56 , 57 , 58 , 59 , 60 , 61 , 62 ] have been obtained by reactions of selenium dihalides with divinyl chalcogenides [ 63 , 64 , 65 ].…”

“…Extending our studies of the reactions of selenium dihalides with linear dienic compounds [ 53 , 54 , 55 , 56 , 57 , 58 , 59 , 60 , 61 , 62 , 66 ], we explored their addition to cyclodienes. The reaction of selenium dihalides with cis , cis -1,5-cyclooctadiene occurred as transannular addition affording 2,6-dihalo-9-selenabicyclo[3.3.1]nonanes in almost quantitative yields ( Scheme 1 ) [ 16 , 67 , 68 ].…”

Reaction of diselenium dichloride with acetylene

“…We perform systematic studies on reactions of selenium halides with acetylenes [2,4,5] and its derivatives, such as divinyl sulfide [6][7][8][9][10], divinyl sulfone [11][12][13][14], and divinyl selenide [15][16][17][18]. Stereoselective methods of synthesis of (E,E)-bis(2-halovinyl) selenides were developed on the basis of reactions of selenium halides with acetylene [4,5].…”