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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