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Synthesis 2007(17): 2699-2705  
DOI: 10.1055/s-2007-983823
PAPER
© Georg Thieme Verlag Stuttgart · New York

Synthesis of Isomeric Enamine Derivatives of Fused Cycloalkeno Thieno[2,3-d]pyrimidin-4(3H)-ones. Stereoelectronic Effect on the Regioselectivity

Annamaria Lilienkampfa, Sami Heikkinena, Ilpo Mutikainenb, Kristiina Wähälä*a
a Laboratory of Organic Chemistry, Department of Chemistry, University of Helsinki, P. O. Box 55, 00014 Helsinki, Finland
Fax: +358(9)19150357; e-Mail: kristiina.wahala@helsinki.fi; e-Mail: annamaria.lilienkampf@helsinki.fi;
b Laboratory of Inorganic Chemistry, Department of Chemistry, University of Helsinki, P. O. Box 55, 00014 Helsinki, Finland
Further Information

Publication History

Received 5 April 2007
Publication Date:
30 July 2007 (online)

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Abstract

A regioselective synthesis of enamine and enaminone derivatives of fused cycloalkeno thieno[2,3-d]pyrimidin-4(3H)-ones is reported. The enamine versus enaminone product in the condensation reaction with N,N-dimethylformamide dimethylacetal (DMFDMA) was shown to depend on the conformation of the cycloalkeno ring fused to the pyrimidinone moiety. The ring conformation and the stereoelectronic effect of the amidine α-protons were studied by X-ray crystallography. In deuterium exchange experiments, the amidine-ketene-N,N-acetal tautomerism was shown to be prohibited with larger (n = 3-4) ring systems consequently yielding the enaminone products.

Key words

regioselectivity - electrophilic additions - imines - ketones - tautomerism

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Crystallographic data has been deposited with the Cambridge Crystallographic Data Centre as supplementary publication numbers CCDC 643240 (3b), CCDC 643241 (3c), CCDC 643242 (3d), and CCDC 643243 (3e). These data can be obtained free of charge from The Cambridge Crystallographic Data Centre via www.ccdc.cam.ac.uk/data_request/cif.