Chemoselective Pd-Based\nDyotropic Rearrangement: Fluorocyclization\nand Regioselective Wacker Reaction of Homoallylic Amides

Fluorocyclization of alkenes tethered with a pronucleophile\nis\nan efficient transformation that converts easily accessible starting\nmaterials to fluorinated heterocycles in a single step. We report\nherein an unprecedented Pd(II)-catalyzed oxidative domino process\nthat transforms homoallylic amides to 5,6-dihydro-4<i>H</i>-1,3-oxazines through a domino oxypalladation/Pd<sup>II</sup>–oxidation/dyotropic\nrearrangement/reductive elimination sequence. Three chemical bonds\nare created under these operationally simple conditions. Taking advantage\nof the facile hydrolysis of the α-fluoro tertiary alkyl ether\nunder acidic conditions, a one-pot conversion of homoallylic amides\nto homologated ketones is subsequently developed, which represents\na rare example of regioselective Wacker oxidation reaction of 1,1-disubstituted\nalkenes.