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 IrIII 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.