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A new approach to 2,2-disubstituted 1-(methylsulfanyl)vinyl phosphonates via an intermediate thiocarbonyl ylide


Mloston, G; Urbaniak, K; Linden, A; Heimgartner, H (2009). A new approach to 2,2-disubstituted 1-(methylsulfanyl)vinyl phosphonates via an intermediate thiocarbonyl ylide. Tetrahedron, 65(39):8191-8198.

Abstract

The reaction of methyl (diethylphosphoryl)dithioformate (6) with diaryldiazomethanes 7a–d in THF at 60 °C to room temperature followed by desulfurization is shown to be a convenient method for the preparation of 2,2-disubstituted 1-(methylsulfanyl)vinyl phosphonates 8a–d. The analogous reactions with 2-diazoacenaphthen-1-one (7f) or 2-diazocamphor (7g) in refluxing THF yield selectively the corresponding (Z)- and (E)-vinyl phosphonates 8f and 8g, respectively. These products can be easily oxidized
to the vinylsulfoxides 13 and vinylsulfones 14. On the other hand, methyl (diethylphosphoryl)dithioformate (6) and 2-diazo-1,2-diphenylethanone (7e) in boiling THF react to give the 1,3-oxathiole 12. All these reactions occur via an intermediate thiocarbonyl ylide 11 followed by 1,3-dipolar electrocyclization and sulfur extrusion or 1,5-dipolar electrocyclization.

Abstract

The reaction of methyl (diethylphosphoryl)dithioformate (6) with diaryldiazomethanes 7a–d in THF at 60 °C to room temperature followed by desulfurization is shown to be a convenient method for the preparation of 2,2-disubstituted 1-(methylsulfanyl)vinyl phosphonates 8a–d. The analogous reactions with 2-diazoacenaphthen-1-one (7f) or 2-diazocamphor (7g) in refluxing THF yield selectively the corresponding (Z)- and (E)-vinyl phosphonates 8f and 8g, respectively. These products can be easily oxidized
to the vinylsulfoxides 13 and vinylsulfones 14. On the other hand, methyl (diethylphosphoryl)dithioformate (6) and 2-diazo-1,2-diphenylethanone (7e) in boiling THF react to give the 1,3-oxathiole 12. All these reactions occur via an intermediate thiocarbonyl ylide 11 followed by 1,3-dipolar electrocyclization and sulfur extrusion or 1,5-dipolar electrocyclization.

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Additional indexing

Item Type:Journal Article, refereed, original work
Communities & Collections:07 Faculty of Science > Department of Chemistry
Dewey Decimal Classification:540 Chemistry
Language:English
Date:26 September 2009
Deposited On:25 Nov 2009 13:10
Last Modified:05 Apr 2016 13:33
Publisher:Elsevier
ISSN:0040-4020
Funders:Polish Ministry of Science and Higher Education, F. Hoffmann-La Roche AG, Basel
Publisher DOI:https://doi.org/10.1016/j.tet.2009.07.074

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