2-Bromomethyl-1,3-thiaselenole in click chemistry: Synthesis of 1-(2,3-dihydro-1,4-thiaselenin-2-yl)-1H-1,2,3-triazoles via copper-catalyzed and thermal 1,3-dipolar cycloaddition with alkynes

• Published in: Journal of organometallic chemistry Vol. 977; pp. 122442 - 122449
• Main Authors: Amosova, Svetlana V., Martynov, Alexander V., Potapov, Vladimir A.
• Format: Journal Article
• Language: English
• Published: LAUSANNE Elsevier B.V 15.10.2022; Elsevier
• Subjects: 2,3-Dihydro-1,4-thiaselenines; 2-Bromomethyl-1,3-thiaselenole; Acetylenes; Chemistry; Chemistry, Inorganic & Nuclear; Chemistry, Organic; Click chemistry; CuAAC; Physical Sciences; Science & Technology; Sodium azide; 2,3-Dihydro-1,4-thiaselenines; Acetylenes; Click chemistry; 2-Bromomethyl-1,3-thiaselenole; Sodium azide; CuAAC; HUISGEN CYCLOADDITION; ARYLSELENIDES; STEPWISE; AZIDE; 2, 3-Dihydro-1, 4-thiaselenines; ORGANOSELENIUM; 1,2,3-TRIAZOLES; RING; EBSELEN; TOXICOLOGY; 2-Bromomethyl-1, 3-thiaselenole
• ISSN: 0022-328X; 1872-8561
• DOI: 10.1016/j.jorganchem.2022.122442

•First representatives of Se/S heterocycles combined with triazoles were obtained.•Regioselective click reactions of 2-azido-2,3-dihydro-1,4-thiaselenine.•Both acetylenic moieties of dipropargyl sulfide were involved in the click reaction. Nucleophilic substitution of bromine in 2-bromomethyl 1,3-thiaselenole with sodium azide occurs at room temperature via an intermediate seleniranium cation with the ring expansion rearrangement to six-membered 2-azido-2,3-dihydro-1,4-thiaselenine in 95% yield. The cycloaddition click reaction of the latter with various terminal acetylenes catalyzed with Cu(OAc)2 in the presence of sodium ascorbate (CuAAC) proceeds regioselectively with the formation of only 1-(2,3-dihydro-1,4-thiaselenin-2-yl)-4-organyl-1H-1,2,3-triazoles in up to 97% yields. In the case of dipropargyl sulfide, the click cycloaddition with both triple bonds is realized at room temperature affording the corresponding bis-adduct in 73% yield. The reaction of 2-azido-2,3-dihydro-1,4-thiaselenine with dimethyl and diethyl acetylenedicarboxylates gives, via the 1,3-dipolar Huisgen cycloaddition, the corresponding 1,4,5-trisubstituted 1,2,3-triazoles, functionalized with the 2,3-dihydro-1,4-thiaselenine ring, in high yields. The obtained products are potentially bioactive compounds and first representatives of 1,2,3-triazoles combined with selenium/sulfur-containing heterocycles. [Display omitted]