Synthesis of diverse substituted pyrimidines through Cu catalyst-controlled Ts group elimination and reinsertion pathway from 2H-azirines with TosMICs

Abstract

Two copper-controlled reactions of 2H-azirines with TosMICs have been developed that provide two efficient and modular approaches to diverse substituted pyrimidines with non-electron-withdrawing substituents at position 4 or 6. The Ts group of TosMIC plays a dual role as the sulfonyl source and the leaving group in the methodologies. Cascade reaction pathways comprising [3 + 2] cycloaddition, ring expansion, Ts group elimination–aromatization, Ts group reinsertion, and oxidative aromatization are also disclosed.