Synthesis of pyrimidine annulated furothiopyrans — An efficient sequential and tandem catalyzed Claisen rearrangement – intramolecular hydroaryloxylation

Abstract

Regioselective synthesis of a hitherto unreported furothiopyran moiety fused at the C-5 and C-6 positions of a pyrimidine heterocycle was achieved by the application of sequential Claisen rearrangement in which a second aromatic Claisen rearrangement and intramolecular hydroaryloxylation were catalyzed by aluminum chloride. The second aromatic Claisen rearrangement step was also studied under thermal conditions to give mostly isomerized exocyclic compounds. The precursor endocyclic compounds were synthesized by thermal [3,3] sigmatropic rearrangement of the corresponding sulfide.Key words: aluminum chloride, sequential Claisen rearrangement, hydroaryloxylation, furothiopyran, pyrimidine.