Rhodium-Catalyzed Synthesis of 2-Aroylpyrimidines via Cascade Heteropolyene Rearrangement
Nikolai Yu. Tiuftiakov, Julia O. Strelnikova, Ilya P. Filippov, Adel R. Khaidarov, Alexander F. Khlebnikov, Alexander S. Bunev, Михаил С. Новиков, Николай В. Ростовский
Abstract
A one-step synthesis of cytotoxic 2-aroylpyrimidines by the denitrogenative reaction of 1-tosyl-1,2,3-triazoles with isoxazoles under rhodium catalysis has been developed. According to the density functional theory calculations and control experiments, the disclosed reaction proceeds via the rearrangement of an oxadiazatetraene intermediate involving a cascade of intramolecular aza-Diels-Alder and retro-aza-Diels-Alder reactions. The presence of a substituent at C4 of the isoxazole is a prerequisite for the formation of the pyrimidines.
Topics & Concepts
ChemistryRhodiumIntramolecular forceSubstituentCascadeCatalysisCope rearrangementIsoxazoleRearrangement reactionCycloadditionCombinatorial chemistryStereochemistryMedicinal chemistryComputational chemistryOrganic chemistryChromatographyCyclopropane Reaction MechanismsCatalytic C–H Functionalization MethodsFluorine in Organic Chemistry