Potassium Base‐Catalyzed Michael Additions of Allylic Alcohols to α,β‐Unsaturated Amides: Scope and Mechanistic Insights.

We report herein the first KHMDS‐catalyzed Michael additions of allylic alcohols to α,β‐unsaturated amides through allylic isomerization. The reaction proceeds smoothly in the presence of only 5 mol% of KHMDS to afford a variety of 1,5‐ketoamides in high yields. Mechanistic investigations, including experimental and computational studies, reveal that the KHMDS‐catalyzed in‐situ generation of the enolate from the allylic alcohol through a tunneling‐assisted 1,2‐hydride shift is the key to the success of this transformation. [ABSTRACT FROM AUTHOR]