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Silylated thiocarbonyl S-methanides as key intermediates in one-pot olefination reactions leading to ferrocenyl-substituted ethenes and dibenzofulvenes


Mloston, Grzegorz; Hamera-Faldyga, Roza; Heimgartner, Heinz (2018). Silylated thiocarbonyl S-methanides as key intermediates in one-pot olefination reactions leading to ferrocenyl-substituted ethenes and dibenzofulvenes. Journal of Sulfur Chemistry, 39(3):267-278.

Abstract

(Trimethylsilyl)diazomethane (TMS-CHN2) reacts smoothly with cycloaliphatic thioketones as well as with fluorene-9-thione at low temperature to give the corresponding 1,3,4-thiadiazole derivatives as product of a regioselective [3+2]-cycloaddition. In the first case, the obtained cycloadducts are relatively stable and eliminate N2 upon heating at 40ºC. In the second case, N2-extrusion occurs already at –40ºC. The silylated thiocarbonyl S-methanides generated thereby can be trapped regioselectively with ferrocenyl hetaryl thioketones to give the sterically crowded 2-silylated 4,4,5,5-tetrasubstituted 1,3-dithiolanes. Without isolation, these products are desilylated with TBAF and tetrasubstituted ethenes or dibenzofulvenes are obtained as final products via cycloelimination (‘[3+2]-cycloreversion’) of the intermediate 1,3-dithiolane carbanion.

Abstract

(Trimethylsilyl)diazomethane (TMS-CHN2) reacts smoothly with cycloaliphatic thioketones as well as with fluorene-9-thione at low temperature to give the corresponding 1,3,4-thiadiazole derivatives as product of a regioselective [3+2]-cycloaddition. In the first case, the obtained cycloadducts are relatively stable and eliminate N2 upon heating at 40ºC. In the second case, N2-extrusion occurs already at –40ºC. The silylated thiocarbonyl S-methanides generated thereby can be trapped regioselectively with ferrocenyl hetaryl thioketones to give the sterically crowded 2-silylated 4,4,5,5-tetrasubstituted 1,3-dithiolanes. Without isolation, these products are desilylated with TBAF and tetrasubstituted ethenes or dibenzofulvenes are obtained as final products via cycloelimination (‘[3+2]-cycloreversion’) of the intermediate 1,3-dithiolane carbanion.

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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:2018
Deposited On:28 Dec 2017 16:30
Last Modified:27 May 2018 05:37
Publisher:Taylor & Francis
ISSN:1741-5993
Funders:National Science Center (Cracow, Poland), Alexander von Humboldt-Stiftung (Bonn, Germany)
Additional Information:This is an Accepted Manuscript of an article published by Taylor & Francis in Journal of Sulfur Chemistry on December 21st, 2017, available online: http://wwww.tandfonline.com/10.1080/17415993.2017.1415339
OA Status:Green
Publisher DOI:https://doi.org/10.1080/17415993.2017.1415339
Project Information:
  • : FunderNational Science Center (Cracow, Poland)
  • : Grant ID
  • : Project Title
  • : FunderAlexander von Humboldt-Stiftung (Bonn, Germany)
  • : Grant ID
  • : Project Title

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