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Bifunctional Iminophosphorane Catalyzed Amide Enolization for Enantioselective Cyclohexadienone Desymmetrization

Charmaine Y. X. Poh, Daniel Rozsar, Jinchao Yang, Kirsten E. Christensen, Darren J. Dixon

2023Angewandte Chemie International Edition14 citationsDOIOpen Access PDF

Abstract

The organocatalytic enolization of 2-arylacetamides, followed by an enantioselective intramolecular conjugate addition to tethered 2,5-cyclohexadienones, yielding 3D fused N-heterocycles, is described. The transformation represents the first strong activating group-free activation of carboxamides via α-C-H deprotonation in a metal-free, catalytic, and enantioselective reaction, and is achieved by employing a bifunctional iminophosphorane (BIMP) superbase.

Topics & Concepts

DesymmetrizationBifunctionalEnantioselective synthesisKeto–enol tautomerismCatalysisAmideChemistryOrganic chemistryAsymmetric Synthesis and CatalysisAsymmetric Hydrogenation and CatalysisSynthetic Organic Chemistry Methods