Projects per year
Abstract
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 prepared by treatment of 1,8-naphthalene dithiols with thionyl chloride and pyridine. The 1,2,3-trithiane-2-oxide ring adopts a and evidence of ring strain (pert-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.
Original language | English |
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Pages (from-to) | 5843-5852 |
Number of pages | 10 |
Journal | Journal of the American Chemical Society |
Volume | 133 |
Issue number | 15 |
Early online date | 28 Mar 2011 |
DOIs | |
Publication status | Published - 20 Apr 2011 |
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Dive into the research topics of 'Sulfur monoxide transfer from peri-substituted trisulfide-2-oxides to dienes: substituent effects, mechanistic studies and application in thiophene synthesis'. Together they form a unique fingerprint.Projects
- 2 Finished
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Harnessing Reactive Intermediates for Organic Synthesis
Grainger, R. (Principal Investigator)
Engineering & Physical Science Research Council
1/10/05 → 31/03/09
Project: Research Councils
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Advanced Research Fellowship: Harnessing Reactive Intermediates for Organic Synthesis
Grainger, R. (Principal Investigator)
Engineering & Physical Science Research Council
1/09/05 → 31/08/10
Project: Research Councils