Deconjugated-Ketone-Derived Dienolates in Remote, Stereocontrolled, Aromative aza-Diels-Alder Cycloaddition

In the manuscript, the application of beta,gamma-unsaturated ketones as precursors of electron-rich dienophiles in the organocatalytic, aromative inverse-electron-demand hetero-Diels-Alder cycloaddition is described. The reaction leads to the formation of biologically relevant benzofuran derivatives bearing additional tetrahydropyridine ring. The reaction is fully site-selective and occurs preferentially at the distal double bond of the dienolate intermediate. Given the absolute configuration assignment a step-wise mechanism has been proposed and the formation of aromatic benzofuran ring indicated as the driving force of the cascade.