Selective Synthesis of Unsymmetrical Aliphatic Acyloins through Oxidation of Iridium Enolates

The first method to access unsymmetrical aliphatic acyloins is presented. The method relies on a fast 1,3-hydride shift mediated by an Ir^III complex in allylic alcohols followed by oxidation with TEMPO⁺ . The direct conversion of allylic alcohols into acyloins is achieved in a one-pot procedure. Further functionalization of the Cα' of the α-amino-oxylated ketone products gives access to highly functionalized unsymmetrical aliphatic ketones, which further highlights the utility of this transformation.