Reaction of selenium dichloride with divinyl telluride

Abstract

SHORT COMMUNICATIONSWe perform systematic studies on reactions of new electrophilic reagents, selenium dichloride and selenium dibromide [1][2][3][4][5], with divinyl chalcogenides and their derivatives. Selenium dihalides react with divinyl sulfide to form 2,6-dihalo-1,4-thiaseleninanes and 5-halo-2-halomethyl-1,3-thiaselenolanes [1]. Addition of selenium dihalides to divinyl selenide gives 4-halo-2-halomethyl-1,3-diselenolanes [2]. By reaction of selenium dihalides with divinyl sulfone we obtained 2,4-bis(halomethyl)-1λ 6 ,3-thiaselenetane and 5-halo-2-halomethyl-1λ 6 ,3-thiaselenolane 1,1-dioxides [3]. In the reaction of selenium dibromide with divinyl ether bis(1,2-dibromoethyl) ether was formed as a result of bromination of both double bonds [4]. Reactions of selenium halides with vinyl tellurides were not reported.We examined the reaction of selenium dichloride with divinyl telluride. Unlike other divinyl chalcogenides, no addition products at the double bond were obtained, while the only product was previously unknown dichloro(divinyl)tellurium (I) which was formed in quantitative yield. tivity, and neither heterocyclic compounds nor addition products at the double bond were detected.Thus the direction of reactions of selenium dihalides with divinyl chalcogenides is largely determined by the chalcogen nature. In the reaction with divinyl telluride, selenium dichloride acts as selective chlorinating agent for tellurium. This is the first example of reactions between compounds containing a selenium-halogen bond and vinyl tellurides.

Reaction of selenium dihalides with allyl benzyl ether

“…Selenium dihalides have been shown to be efficient and selective reagents in the synthesis of organoselenium compounds. Although neither selenium dichloride nor selenium dibromide can be isolated in the pure state [1], these reagents can be generated in situ and involved in various transformations [2][3][4][5][6][7][8][9][10][11][12][13][14].…”

“…We perform systematic studies on reactions of selenium dichloride and dibromide with unsaturated compounds [5][6][7][8][9][10][11][12][13][14]. The reaction of selenium dihalides with vinyl ethers gave the corresponding Markovnikov adducts, bis(2-halo-2-organyloxyethyl) selenides, in high yield [8,9].…”

“…The reactions of selenium dichloride and dibromide with diallyl ether, diallyl sulfide, and diallyl selenide led to the formation of sixmembered heterocycles, 3,5-bis(halomethyl)-1,4-chalcogenaselenanes, whose structure corresponds to the anti-Markovnikov addition [10][11][12]. The reactions of selenium dihalides with divinyl and diallyl tellurides involved halogenation of the tellurium atom [13,14].…”

“…Selenium dihalides have been shown to be efficient and selective reagents in the synthesis of organoselenium compounds. Although neither selenium dichloride nor selenium dibromide can be isolated in the pure state [1], these reagents can be generated in situ and involved in various transformations [2][3][4][5][6][7][8][9][10][11][12][13][14].We perform systematic studies on reactions of selenium dichloride and dibromide with unsaturated compounds [5][6][7][8][9][10][11][12][13][14]. The reaction of selenium dihalides with vinyl ethers gave the corresponding Markovnikov adducts, bis(2-halo-2-organyloxyethyl) selenides, in high yield [8,9].…”

“…The reactions of selenium dichloride and dibromide with diallyl ether, diallyl sulfide, and diallyl selenide led to the formation of sixmembered heterocycles, 3,5-bis(halomethyl)-1,4-chalcogenaselenanes, whose structure corresponds to the anti-Markovnikov addition [10][11][12]. The reactions of selenium dihalides with divinyl and diallyl tellurides involved halogenation of the tellurium atom [13,14].In continuation of our studies on reactions of selenium dihalides with unsaturated chalcogenides [5][6][7][8][9][10][11][12][13][14], the present communication reports on the reaction of selenium dichloride and dibromide with allyl benzyl ether (I). The reactions were carried out in carbon tetrachloride or chloroform at room temperature, and the products were the corresponding anti-Markovnikov adducts, bis(3-benzyloxy-1-halopropan-2-yl) selenides II and III, which underwent gradual rearrangement into thermodynamically more stable Markovnikov adducts IV and V. Conditions ensuring selective formation of compounds IV and V in high yield were found.…”