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Reactions of polycyclic thioketones with a phosphonylated carbanion


Mloston, G; Obijalska, E; Urbaniak, K; Heimgartner, H (2008). Reactions of polycyclic thioketones with a phosphonylated carbanion. Heteroatom Chemistry, 19(2):182-187.

Abstract

ABSTRACT: Polycyclic, non enolizable cycloaliphatic thioketones 1a and 1b react smoothly with the lithium salt of diethyl methylphosphonate 7 in THF solution at –40°C to afford products of the carbophilic attack exclusively. Quenching of the obtained lithium thiolates with alkyl iodides yields sulfanes of type 9 or 11, respectively, in good yields. 1-Fluoro-2,4-dinitrobenzene was shown to act as an arylating agent. In the case of the ‘cage’ thioketone 1b, the carbanion of salt 7 approaches the C=S bond from the exo-side exclusively. In contrast to the parent carbonyl compounds, thioketones 1 show no tendency to undergo the conversion analogous to the Horner-Wadsworth-Emmons reaction, which would result in the formation of an olefinic product.

Abstract

ABSTRACT: Polycyclic, non enolizable cycloaliphatic thioketones 1a and 1b react smoothly with the lithium salt of diethyl methylphosphonate 7 in THF solution at –40°C to afford products of the carbophilic attack exclusively. Quenching of the obtained lithium thiolates with alkyl iodides yields sulfanes of type 9 or 11, respectively, in good yields. 1-Fluoro-2,4-dinitrobenzene was shown to act as an arylating agent. In the case of the ‘cage’ thioketone 1b, the carbanion of salt 7 approaches the C=S bond from the exo-side exclusively. In contrast to the parent carbonyl compounds, thioketones 1 show no tendency to undergo the conversion analogous to the Horner-Wadsworth-Emmons reaction, which would result in the formation of an olefinic product.

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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:March 2008
Deposited On:06 Feb 2009 13:18
Last Modified:06 Dec 2017 17:44
Publisher:Wiley-Blackwell
ISSN:1042-7163
Funders:Rector of the University of Lodz, F. Hoffmann-La Roche AG, Basel
Additional Information:The attached file is a preprint (accepted version) of an article published in Heteroatom Chemistry 2008, 19(2):182-187
Publisher DOI:https://doi.org/10.1002/hc.20390

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