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Novel Trifluoromethylated Spiro-1,3,4-thiadiazoles via (3+2)-Cycloadditions of 2,3-Diphenylcyclopropenethione with Selected in Situ-Generated Nitrile Imines Derived from Trifluoroacetonitrile


Utecht-Jarzynska, Greta; Jasinski, Marcin; Swiatek, Kamil; Mloston, Grzegorz; Heimgartner, Heinz (2019). Novel Trifluoromethylated Spiro-1,3,4-thiadiazoles via (3+2)-Cycloadditions of 2,3-Diphenylcyclopropenethione with Selected in Situ-Generated Nitrile Imines Derived from Trifluoroacetonitrile. Heterocycles:Epub ahead of print.

Abstract

The in situ-generated N-aryl nitrile imines derived from trifluoroacetonitrile react efficiently with 2,3-diphenylcyclopropenethione to give spirocyclic 1,3,4-thiadiazole derivatives as products of a regio- and chemoselective (3+2)-cycloaddition in good to excellent yields. A stepwise mechanism via initial nucleophilic attack of the S-atom onto the electrophilic C-atom of the electron-deficient 1,3-dipole leading to a zwitterionic intermediate is postulated to explain these formal (3+2)-cycloaddition reactions. The presence of the CF3 group is necessary to activate the nitrile imine for the efficient trapping of the cyclopropenethione. These are the first examples of a successful reaction of this C=S dipolarophile affording 1,3,4-thiadiazoles as formal (3+2)-cycloadducts.

Abstract

The in situ-generated N-aryl nitrile imines derived from trifluoroacetonitrile react efficiently with 2,3-diphenylcyclopropenethione to give spirocyclic 1,3,4-thiadiazole derivatives as products of a regio- and chemoselective (3+2)-cycloaddition in good to excellent yields. A stepwise mechanism via initial nucleophilic attack of the S-atom onto the electrophilic C-atom of the electron-deficient 1,3-dipole leading to a zwitterionic intermediate is postulated to explain these formal (3+2)-cycloaddition reactions. The presence of the CF3 group is necessary to activate the nitrile imine for the efficient trapping of the cyclopropenethione. These are the first examples of a successful reaction of this C=S dipolarophile affording 1,3,4-thiadiazoles as formal (3+2)-cycloadducts.

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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:25 September 2019
Deposited On:26 Sep 2019 09:58
Last Modified:27 Sep 2019 11:25
Publisher:Elsevier
ISSN:0385-5414
OA Status:Closed
Publisher DOI:https://doi.org/10.3987/COM-19-S(F)20
Official URL:https://www.heterocycles.jp/newlibrary/downloads/PDF/26251/101/0
Related URLs:https://www.heterocycles.jp/newlibrary/libraries/prepress
Project Information:
  • : FunderNational Science Center (Cracow, Poland)
  • : Grant ID2016/21/N/ST5/01254
  • : Project Title

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