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

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.

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

“…The first synthesis of organose-lenium compounds from selenium dichloride and dibromide is the preparation of 1,4selenasilafulvenes by the cyclization reaction of these reagents with dimethyldiethynylsilane [52]. The selectivity and efficiency of the use of selenium dichloride and dibromide in organic synthesis have been shown in many reactions, which made it possible to obtain previously unknown classes of organoselenium compounds and study their chemical properties [53][54][55][56][57][58][59][60][61][62][63][64][65][66]. Compounds with high glutathione peroxidase-like activity have been found [56].…”

“…The use of selenium dichloride and dibromide made it possible to discover new possibilities in organic synthesis [53][54][55][56][57][58][59][60][61][62][63][64][65][66]. The reaction of selenium dichloride with divinyl sulfide at −50 • C in chloroform gave six-membered heterocycle, 2,6-dichloro-1,4-thiaselenane (1) (a 6/1 diastereomer ratio), in quantitative yield, which underwent rearrangement (chloroform, room temperature) to a five-membered heterocycle, 5-chloro-2-chloromethyl-1,3thiaselenolane (2) in 61% yield (a 2/1 diastereomer ratio).…”