Palladium-Catalyzed Aminomethylation and Cyclization of Enynol to O-Heterocycle Confined 1,3-Dienes

The rational tuning of the electrophilicity of the allylpalladium intermediates enables the regioselectively intramolecular 1,2-addition of enynol in the presence of aminal. This aminomethylation and cyclization reaction via C–N bond activation and intramolecular nucleophilic addition provides a rare example for the synthesis of O-containing heterocycle-confined 1,3-dienes, which is of synthetic potential for further derivatization. The method possesses broad substrate generality as well as functional group compatibility and efficiently affords a wide range of desired products with 5-, 6-, and 8-membered O-containing heterocycles with various functional groups.