Skeletal Editing of Ketones by Azide-Enolate Cycloaddition-Rearrangement

<jats:p>Direct skeletal editing of unmodified ketones is achieved using an azide-enolate cycloaddition-rearrangement process. The reaction was applicable to a wide range of diverse cyclic and acyclic substrates, showed high stereoselectivity, and regioselectivity was tuneable by choice of enolate formation conditions. Experimental and computational mechanistic studies were carried out to probe mechanistic aspects of the rearrangement processes. We anticipate this method to be particularly useful for the diversification of complex bioactive compounds.</jats:p>