Sulfur monoxide transfer from peri-substituted trisulfide-2-oxides to dienes: substituent effects, mechanistic studies and application in thiophene synthesis
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 t...
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| Format: | Article |
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American Chemical Society
2011
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| author | Grainger, Richard S. Patel, Bhaven Kariuki, Benson M. Male, Louise Spencer, Neil |
| author_facet | Grainger, Richard S. Patel, Bhaven Kariuki, Benson M. Male, Louise Spencer, Neil |
| author_sort | Grainger, Richard S. |
| collection | LMU |
| description | 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. |
| first_indexed | 2024-07-09T03:46:09Z |
| format | Article |
| id | oai:repository.londonmet.ac.uk:1044 |
| institution | London Metropolitan University |
| last_indexed | 2024-07-09T03:46:09Z |
| publishDate | 2011 |
| publisher | American Chemical Society |
| record_format | eprints |
| spelling | oai:repository.londonmet.ac.uk:10442022-12-02T09:33:21Z https://repository.londonmet.ac.uk/1044/ 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 540 Chemistry & allied sciences 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. American Chemical Society 2011-03-28 Article PeerReviewed Grainger, Richard S., Patel, Bhaven, Kariuki, Benson M., Male, Louise and Spencer, Neil (2011) Sulfur monoxide transfer from peri-substituted trisulfide-2-oxides to dienes: substituent effects, mechanistic studies and application in thiophene synthesis. Journal of the American Chemical Society, 133 (15). pp. 5843-5852. ISSN 0002-7863 http://dx.doi.org/10.1021/ja108865w doi:10.1021/ja108865w doi:10.1021/ja108865w |
| spellingShingle | 540 Chemistry & allied sciences Grainger, Richard S. Patel, Bhaven Kariuki, Benson M. Male, Louise Spencer, Neil Sulfur monoxide transfer from peri-substituted trisulfide-2-oxides to dienes: substituent effects, mechanistic studies and application in thiophene synthesis |
| title | Sulfur monoxide transfer from peri-substituted trisulfide-2-oxides to dienes: substituent effects, mechanistic studies and application in thiophene synthesis |
| title_full | Sulfur monoxide transfer from peri-substituted trisulfide-2-oxides to dienes: substituent effects, mechanistic studies and application in thiophene synthesis |
| title_fullStr | Sulfur monoxide transfer from peri-substituted trisulfide-2-oxides to dienes: substituent effects, mechanistic studies and application in thiophene synthesis |
| title_full_unstemmed | Sulfur monoxide transfer from peri-substituted trisulfide-2-oxides to dienes: substituent effects, mechanistic studies and application in thiophene synthesis |
| title_short | Sulfur monoxide transfer from peri-substituted trisulfide-2-oxides to dienes: substituent effects, mechanistic studies and application in thiophene synthesis |
| title_sort | sulfur monoxide transfer from peri substituted trisulfide 2 oxides to dienes substituent effects mechanistic studies and application in thiophene synthesis |
| topic | 540 Chemistry & allied sciences |
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