Deconjugated‐Ketone‐Derived Dienolates in Remote, Stereocontrolled, Aromative <i>aza</i>‐Diels‐Alder Cycloaddition
Sebastian Frankowski, Anna Skrzyńska, Lesław Sieroń, Łukasz Albrecht
Abstract
Abstract In the manuscript, the application of β,γ‐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. magnified image
Topics & Concepts
ChemistryCycloadditionBenzofuranKetoneRing (chemistry)Diels–Alder reactionStereochemistryMedicinal chemistryComputational chemistryOrganic chemistryCatalysisAsymmetric Synthesis and CatalysisOxidative Organic Chemistry ReactionsCyclopropane Reaction Mechanisms