Stereoselective Capture of N-Acyliminium Ions Generated from α-Hydroxy-N-acylcarbamides: Direct Synthesis of Uracils from Barbituric Acids Enabled by SmI2 Reduction

Lewis acid promoted cleavage of α-amino alcohols derived from barbituric acids via chemoselective Sm(II)-mediated electron transfer affords a wide range of C6-substituted 5,6-dihydrouracils. The reaction involves the first generation of N-acyliminium ions directly from the versatile barbituric acids and proceeds with excellent stereoselectivity. The products are shown to be active in generic transition metal catalyzed reactions, thus providing a modular and highly practical sequence to the biologically significant uracil derivatives.