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Synthesis 2007(18): 2839-2848  
DOI: 10.1055/s-2007-983834
PAPER
© Georg Thieme Verlag Stuttgart · New York

Synthesis and Structure of Thia and Selena Heterocycles Containing Cycloamidine Substructures

Jan Fleischhauera, Rainer Beckert*a, Wolfgang Günthera, Stefan Klugea, Stefan Zahna, Jennie Westona, Dorothea Bergb, Helmar Görlsc
a Institute of Organic and Macromolecular Chemistry, Friedrich Schiller University, Humboldtstrasse 10, 07743 Jena, Germany
b Institute of Physical Chemistry, Friedrich Schiller University, Lessingstrasse 10, 07743 Jena, Germany
c Institute of Inorganic and Analytical Chemistry, Friedrich Schiller University, Lessingstrasse 8, 07743 Jena, Germany
e-Mail: Rainer.Beckert@uni-jena.de;
Further Information

Publication History

Received 23 May 2007
Publication Date:
08 August 2007 (online)

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Abstract

Cyclization of a bis-arylimidoyl chloride with an acylselenourea leads to the construction of a 1,3-selenazolidine with a heteroradialene structure. Another reaction of the bis-arylimidoyl chloride (hydrazinolysis) leads to the formation of Δ2-1,2-diazetines, which we have shown previously to be reactive precursors for ring transformation reactions that yield unusual heterocycles. We now demonstrate that the reaction of these Δ2-1,2-diazetines with various isothio- or isoselenocyanates affords an efficient entry to highly substituted 1,3,4-thia- or -selenadiazines. The structures of these novel derivatives were confirmed by NMR and mass spectroscopy, elemental analysis, and X-ray structural analysis. Detailed multidimensional 77Se NMR experiments as well as density functional theory (DFT) calculations show structural specifics of these compounds.

Key words

ring expansion - heterocycles - selenium - sulfur - non­covalent chalcogen interactions

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Orca - an ab initio, DFT, and semiempirical scf-mo package; see: http://www.thch.uni-bonn.de/tc/orca.

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Weinhold, F. NBO, version 5; see:
http://www.chem.wisc.edu/˜nbo5/.

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CCDC-644462 (3), CCDC-644463 (7g), and CCDC-644464 (8j) contain the supplementary crystallographic data for this paper. These data can be obtained free of charge via www.ccdc.cam.ac.uk/conts/retrieving.html (or from the Cambridge Crystallographic Data Centre, 12 Union Road, Cambridge CB2 1EZ, UK; fax: +44(1223)336033; email: deposit@ccdc.cam.ac.uk).