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 Naoki Kise Yusuke Hamada Toshihiko Sakurai 10.1021/acs.joc.6b00670.s004 https://acs.figshare.com/articles/dataset/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_/3405307 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. 2016-05-12 00:00:00 adduct ci presence dimethyluracil Aromatic Ketones Electroreductive Intermolecular methyl 1 H NMR spectra Substituted DMAP Disubstituted Dihydro desilylated alcohols tran disubstituted TBAF dihydro