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Formation of phosphonylated thiiranes in the reaction of a diazomethanephosphonate and cycloaliphatic thioketones


Mloston, G; Urbaniak, K; Lesniak, S; Wasiak, P; Heimgartner, H (2007). Formation of phosphonylated thiiranes in the reaction of a diazomethanephosphonate and cycloaliphatic thioketones. Heterocycles, 72(1):541-552.

Abstract

The reaction of diethyl diazomethanephosphonate (1) with cycloaliphatic thioketones (6) in THF at room temperature leads to the corresponding thiirane-2-phosphonates (7) in good yield. A reaction mechanism via 1,3-dipolar cycloaddition of the diazo compound with the C=S group to give the 2,5-dihydro-1,3,4-thiadiazole-2-phosphonate as an intermediate, which
spontaneously eliminates nitrogen is most likely. The resulting thiocarbonyl ylide undergoes a 1,3-dipolar electrocyclization to yield a thiirane. These products can be desulfurized smoothly by treatment with tris(diethylamino)phosphine to give alpha,beta-unsaturated phosphonates.

Abstract

The reaction of diethyl diazomethanephosphonate (1) with cycloaliphatic thioketones (6) in THF at room temperature leads to the corresponding thiirane-2-phosphonates (7) in good yield. A reaction mechanism via 1,3-dipolar cycloaddition of the diazo compound with the C=S group to give the 2,5-dihydro-1,3,4-thiadiazole-2-phosphonate as an intermediate, which
spontaneously eliminates nitrogen is most likely. The resulting thiocarbonyl ylide undergoes a 1,3-dipolar electrocyclization to yield a thiirane. These products can be desulfurized smoothly by treatment with tris(diethylamino)phosphine to give alpha,beta-unsaturated phosphonates.

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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:2007
Deposited On:04 Nov 2011 14:10
Last Modified:05 Apr 2016 15:04
Publisher:The Japan Institute of Heterocyclic Chemistry
ISSN:0385-5414
Funders:Rector of the University of Lodz (grants 505/712 and 505/710), F. Hoffmann-La Roche AG, Basel
Publisher DOI:https://doi.org/10.3987/COM-06-S(K)47

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