Pd(II)/PIDA‐Enabled Migratory Triple Functionalization of Terminal Alkenes via a 1,2‐C/Pd(IV) Dyotropic Rearrangement

Abstract We report a Pd(II)‐catalyzed migratory triple functionalization of terminal alkenes. The reaction of homoallylic amides with phenyliodine(III) diacetate (PIDA) under Pd(II) catalysis delivers 6‐acetoxylated 5,6‐dihydro‐4 H ‐1,3‐oxazines through the formation of one C─C and two C─O bonds. Mechanistic studies suggest a sequence involving oxypalladation, oxidation of Pd(II) to Pd(IV), a 1,2‐alkyl(aryl)/Pd(IV) dyotropic rearrangement (DR), and subsequent acetoxylation. While Pd(II)/Pd(IV) catalysis with PIDA as the oxidant has enabled numerous powerful transformations, the DR reported here is unprecedented.