Cationic Pd(IV)-Induced Highly Diastereoselective Arylative Cascade Cyclization of Allene-Tethered Cyclohexadienones Leading to Oxygenated Bicyclic Motifs.

A cationic Pd(IV)-catalyzed arylative hydroxylation-Micheal addition of allenyl-tethered cyclohexadienones was developed. This relay reaction could afford highly diastereoselective various functionalized arylative 1,4-dioxane cis-bicyclic structural units with good to high yields. The striking features revealed from these studies is the necessity of Selectfluor and the oxidative hydroxylation originating from water initiated by F-Pd(IV) catalysis. A plausible mechanism was also proposed for this variant observation.