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

Annamaria Lilienkampf; Sami Heikkinen; Ilpo Mutikainen; Kristiina Wähälä

doi:10.1055/s-2007-983823

PAPER

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

Annamaria Lilienkampf^a, Sami Heikkinen^a, Ilpo Mutikainen^b, 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

Abstract

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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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References

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