Regio- and stereoselective synthesis of ( Z )-(2,3-dihydro-1,4-thiaselenin-2-yl) vinyl sulfides from 2-bromomethyl-1,3-t
- PDF / 199,008 Bytes
- 4 Pages / 594 x 792 pts Page_size
- 24 Downloads / 159 Views
Regio- and stereoselective synthesis of (Z)-(2,3-dihydro-1,4-thiaselenin-2-yl) vinyl sulfides from 2-bromomethyl-1,3-thiaselenole under phase-transfer catalysis conditions Andrey S. Filippov1, Svetlana V. Amosova1, Vladimir A. Potapov1* 1
Favorsky Irkutsk Institute of Chemistry, Siberian Branch of the Russian Academy of Sciences, 1 Favorsky St., Irkutsk 664033, Russia; e-mail: [email protected] Submitted July 10, 2020 Accepted after revision September 29, 2020
Translated from Khimiya Geterotsiklicheskikh Soedinenii, 2020, 56(9), 1237–1240
A one-pot regio- and stereoselective method for the synthesis of previously unknown (Z)-(2,3-dihydro-1,4-thiaselenin-2-yl) vinyl sulfides based on 2-bromomethyl-1,3-thiaselenole and activated acetylenes at room temperature under phase-transfer catalysis conditions in 90– 96% yields has been developed. Keywords: activated acetylenes, 2-bromomethyl-1,3-thiaselenole, vinyl sulfides, 2,3-dihydro-1,4-thiaselenines, nucleophilic addition.
It has been established that selenium deficiency in human body increases the probability of stroke, cardiovascular pathologies, cancer, arthritis, and many other diseases.1 Glutathione peroxidase is known seleniumcontaining enzyme the action of which lowers the concentration of peroxide compounds in the body and reduces the risk of many diseases.1 Some seleniumcontaining heterocycles exhibit an effect similar to glutathione peroxidase, as well possess antitumor, antibacterial, and antiviral activity.2,3 It has been shown that 1,4-thiaselenines and their analogs exhibit antitumor and antibacterial activity.3 Dihydro-1,4-thiaselenines are very rare class of compounds, until recent years,4 only two representatives were known (5-methyl- and 5-ethyl-2,3-dihydro1,4-thiaselenines) obtained by the reaction of 1-(2-chloroethylsulfanyl)-1-alkyne with lithium selenide in 60 and 64% yields, respectively.5 (Dihydrothiaselenin-2-yl) vinyl sulfides are not described in the literature. The development of methods for the selective introduction of a selenium atom into an organic molecule is an important task in the chemistry of organoelement compounds. Based on selenium dibromide and divinyl sulfide, we have developed one-pot method for the preparation of 2-bromomethyl-1,3-thiaselenole,6 a new highly 0009-3122/20/56(9)-1237©2020 Springer Science+Business Media, LLC
reactive reagent whose nucleophilic substitution reactions are accompanied by ring opening or rearrangements.4,7 In this work, we have proposed a one-pot regio- and stereoselective method for the synthesis of (Z)-2,3-dihydro1,4-thiaselenin-2-yl) vinyl sulfides from 2-bromomethyl1,3-thiaselenole and activated acetylenes: methyl and ethyl propiolates, phenyl ethynyl ketone, dimethyl and diethyl acetylenedicarboxylates under phase-transfer catalysis conditions. Phase-transfer catalysis is often used for nucleophilic substitution of thiolate anions, but it is rarely applied for the addition of the thiolate anions to a triple bond.8 In the first experiments, we carried out the interaction of 2-bromomet
Data Loading...
