Description

• Title:
  On the strong difference in reactivity of acyclic and cyclic diazodiketones with thioketones: experimental results and quantum-chemical interpretation
• Creator:
  Mereshchenko, Andrey S.;
  Ivanov, Alexey V.;
  Baranovskii, Viktor I.;
  Mloston, Grzegorz;
  Rodina, Ludmila L.;
  Nikolaev, Valerij A.
• Contributor:
  Mereshchenko Andrey S., Institute of Chemistry, Saint Petersburg State University;
  Ivanov Alexey V., Institute of Chemistry, Saint Petersburg State University;
  Baranovskii Viktor I., Institute of Chemistry, Saint Petersburg State University;
  Mloston Grzegorz, Faculty of Chemistry, University of Łódź,;
  Nikolaev Valerij A., Institute of Chemistry, Saint Petersburg State University;
  gmloston@uni.lodz.pl;
  valerij.nikolaev@gmail.com
• Description:
  The 1,3-dipolar cycloaddition of acyclic 2-diazo-1,3-dicarbonyl compounds (DDC) and thioketones preferably occurs with Z,Econformers and leads to the formation of transient thiocarbonyl ylides in two stages. The thermodynamically favorable further transformation of C=S ylides bearing at least one acyl group is identified as the 1,5-electrocyclization into 1,3-oxathioles. However, in the case of diazomalonates, the dominating process is 1,3-cyclization into thiiranes followed by their spontaneous desulfurization yielding the corresponding alkenes. Finally, carbocyclic diazodiketones are much less reactive under similar conditions due to the locked cyclic structure and are unfavorable for the 1,3-dipolar cycloaddition due to the Z,Z-conformation of the diazo molecule. This structure results in high, positive values of the Gibbs free energy change for the first stage of the cycloaddition process.;
  A. V. I. thanks the Saint Petersburg State University for financial support of his stay at the University of Łódź with Prof. G. Mloston (order 1831/1; 02.06.2011). A. S. M. acknowledges the Saint Petersburg State University for financial support in the form of a postdoctoral fellowship (No. 12.50.1562.2013). G. M. acknowledges support by the National Science Center (PLCracow) within the Grant Maestro–3 (Dec–2012/06/A/ST5/ 00219). The calculations were performed with the assistance of the Saint Petersburg State University Computer Center and the Chemistry Department of Saint Petersburg State University.
• Object availability:
  free access
• Rights:
  Uznanie autorstwa 3.0 Polska;
  http://creativecommons.org/licenses/by/3.0/pl
• Date:
  2015.09.24;
  2015.04.20
• Type:
  Article
• Language:
  English
• Format:
  application/pdf
• Publisher:
  Beilstein Institute for the Advancement of Chemical Sciences
• Relation:
  Beilstein Journal of Organic Chemistry;2015;
  11
• Subject:
  diazocarbonyl compounds;
  1,3-dipolar cycloaddition;
  1,3-oxathioles;
  thiiranes;
  thiocarbonyl ylides;
  thioketones
• Identifier:
  1860-5397;
  http://hdl.handle.net/11089/11930 ;
  10.3762/bjoc.11.57
• Data provider:
  Repozytorium Uniwersytetu Łódzkiego
• Can I use it?:
  check license
• Type:
  image