Bismuth(III) triflate catalyzed tandem esterification–Fries–oxa-Michael route to 4-chromanones

Abstract An efficient tandem reaction approach is described to prepare 4-chromanones from electron-rich phenols and 3,3-dimethylacrylic acid or trans -crotonic acid in boiling toluene using 20 mol % bismuth(III) triflate as the catalyst. The reaction is also successful from the corresponding aryl esters of each of these acids under the same conditions. The procedure is convenient to perform, and 25–90% yields of products are realized following chromatography. A range of substrates is included (14 substrates for each acid) to help define the scope of the process. Additional experiments are reported, which confirm that the sequence of events involves (1) esterification, (2) Fries rearrangement and (3) oxa-Michael ring closure.