Electroreductive Intermolecular Coupling of Uracils with Aromatic Ketones: Synthesis of 6‑Substituted and <i>cis</i>-5,6-Disubstituted 5,6-Dihydro-1,3-dimethyluracils and Their Transformation to 6‑Substituted 1,3-Dimethyluracils, <i>trans</i>-5,6-Disubstituted 5,6-Dihydro-1,3-dimethyluracils, and 4,5,5-Trisubstituted 3‑Methyloxazolizin-2-ones
2016-05-12T00:00:00Z (GMT) by
The electroreductive coupling of 1,3-dimethyluracil, thymine, and 5-fluorouracil with aromatic ketones in the presence of TMSCl gave 6-substituted and <i>cis</i>-5,6-disubstituted 5,6-dihydro-1,3-dimethyluracils. The dehydrotrimethylsiloxylation of the adducts afforded 6-substituted and 5,6-fused 1,3-dimethyluracils. The detrimethylsilylation of the adducts with TBAF or 1 M HCl–MeOH gave 4,5,5-trisubstituted 3-methyloxazolizin-2-ones or 3-methyloxazolizin-2-imines in addition to simply desilylated alcohols. The <i>cis</i>-5,6-disubstituted 5,6-dihydro-1,3-dimethyluracils were isomerized to the corresponding <i>trans</i>-isomers by heating in the presence of cat. DMAP. The <i>cis</i>- and <i>trans</i>-5,6-disubstituted 5,6-dihydro-1,3-dimethyluracils were assigned by the coupling constants <i>J</i><sub>5,6</sub> of their <sup>1</sup>H NMR spectra.