Highly Site-Selective Metal-Free C-H Acyloxylation of Stable Enamines

A highly site-selective acyloxylation of stable enamines with PhI(OAc)₂ under metal-free conditions to afford (E)-vinyl acetate derivatives in good to excellent yields is described. Depending on the judicious choice of the solvent system, either the α- or β-site-selective product could be obtained with high selectivity. For the α-site-selective product, the rearranged amide compound is obtained as the major product. This reaction proceeds under mild reaction conditions (room temperature, metal-free, and open-flask) and features a broad substrate scope.