18015-16-2Relevant academic research and scientific papers
[1 + 2] Cycloadditions of sulfur monoxide (SO) to alkenes and alkynes and [1 + 4] cycloadditions to dienes (polyenes). Generation and reactions of singlet SO?
Nakayama, Juzo,Tajima, Yumi,Xue-hua, Piao,Sugihara, Yoshiaki
, p. 7250 - 7251 (2007)
The Diels-Alder adduct, produced from 3,4-di-tert-butylthiophene 1-oxide and dimethyl acetylenedicarboxylate, spontaneously extrudes sulfur monoxide (SO) at room temperature and serves as a new method for generation of SO under mild conditions. Thus, the SO generated underwent [1 + 2] cycloadditions to a series of alkenes and alkynes to produce thiirane oxides and thiirene 1-oxides, respectively, providing new syntheses of the sulfur-containing three-membered heterocycles. The SO also reacted with a variety of cyclic and acyclic dienes to give the corresponding 2,5-dihydrothiophene 1-oxides. Copyright
A novel recyclable sulfur monoxide transfer reagent
Grainger, Richard S.,Procopio, Alberto,Steed, Jonathan W.
, p. 3565 - 3568 (2001)
(matrix presented) Trisulfide 2-oxide 11 has been prepared from disulfide 9 via reduction to the corresponding dithiol and subsequent trapping with thionyl chloride. Heating trisulfide oxide 11 in the presence of dienes results in transfer of sulfur monoxide to form cyclic unsaturated sulfoxides 13 in good to excellent yields, along with recovery of disulfide 9. A Pummerer reaction can be used to convert the cyclic sulfoxides into thiophenes.
A useful precursor for sulfur monoxide transfer
Abu-Yousef, Imad A.,Harpp, David N.
, p. 201 - 204 (1995)
When triphenylmethanesulfenyl chloride (8) (or its thio 9 and dithio 10 homolog) is treated with adamantylideneadamantane (11), adamantylideneadamantn thiirane (12) is produced (92%). Compound 12 was treated with m-chloroperoxybenzoic acid (m-CPBA) forming adamantylideneadamantane thiirane 1-oxide (13) in 99% isolated yield. The structures of 12 and 13 were established by 1H and 13C NMR, mass spectrometry as well as by X-ray analysis. Sulfoxide 13 decomposes smoothly to deliver sulfur monoxide in good yield to various dienes.
Sulfur monoxide transfer from peri -substituted trisulfide-2-oxides to dienes: Substituent effects, mechanistic studies and application in thiophene synthesis
Grainger, Richard S.,Patel, Bhaven,Kariuki, Benson M.,Male, Louise,Spencer, Neil
supporting information; experimental part, p. 5843 - 5852 (2011/06/22)
Three peri-substituted trisulfide-2-oxides are prepared by treatment of 1,8-naphthalene dithiols with thionyl chloride and pyridine. The 1,2,3-trithiane-2-oxide ring adopts a sofa conformation in the solid state, with a pseudoaxial oxygen and evidence of ring strain (peri-interaction). Heating the trisulfide-2-oxides in the presence of a diene results in formal sulfur monoxide (SO) transfer to form unsaturated cyclic sulfoxides, along with a recyclable 1,8-naphthalene disulfide. The presence of o-methoxy or o-tert-butyl substituents on the naphthalene ring lowers the temperature and increases the rate at which SO transfer occurs. Trapping experiments and kinetic studies are consistent with the generation of triplet SO, followed by in situ trapping by diene. Transfer of SO also occurs upon irradiation at room temperature, but yields of sulfoxide are lower. Dehydration of the sulfoxides under Pummerer conditions gives thiophenes, including the naturally occurring thioperillene. Two dienes form thiophenes directly under the SO transfer conditions. The methodology is applied in a formal synthesis of the antiplatelet medication Plavix.
Recent chemistry of the chalcogen diatomics
Tardif, Sylvie L.,Rys, Andrzej Z.,Abrams, Charles B.,Abu-Yousef, Imad A.,Leste-Lasserre, Pierre B. F.,Schultz, Erwin K. V.,Harpp, David N.
, p. 12225 - 12236 (2007/10/03)
The chemistry of the generation and trapping of diatomic sulfur (S2) and sulfur monoxide (SO) are reviewed with special emphasis on recent work, including initial efforts to detect and trap diatomic selenium (Se2).
Effective Precursors for Sulfur Monoxide Formation
Abu-Yousef, Imad A.,Harpp, David N.
, p. 8366 - 8371 (2007/10/03)
When triphenylmethanesulfenyl chloride (12) (or its thio 13 or dithio homolog 14) are treated with hindered olefins 15 and 16, thiiranes 10 and 11 are produced in high isolated yields (ca. 94%). Treatment of 10 and 11 with m-chloroperoxybenzoic acid (m-CPBA) leads to the formation of thiirane 1-oxides 8 and 9 (99% isolated yields). The structures of 8-11 were established by 1H and 13C NMR, mass spectrometry as well as by X-ray. Thermal decomposition of either 8 or 9 smoothly delivers sulfur monoxide to various 1,3-dienes giving cyclic sulfoxides in good yield. A variety of conditions were employed to optimize the yield of the trapped adducts.
