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An Aza-Enolate Strategy Enables Iridium-Catalyzed Enantioselective Hydroalkenylations of Minimally Polarized Alkenes en Route to Complex N-Aryl β<sup>2</sup>-Amino Acids

Fenglin Hong, Craig M. Robertson, John F. Bower

2024Journal of the American Chemical Society18 citationsDOIOpen Access PDF

Abstract

High Resolution Image Download MS PowerPoint Slide Cationic Ir(I)-complexes modified with homochiral diphosphines promote the hydroalkenylative cross-coupling of β-(arylamino)acrylates with monosubstituted styrenes and α-olefins. The processes are dependent on the presence of an NH unit, and it is postulated that metalation of this generates an iridium aza-enolate that engages the alkene during the C–C bond forming event. The method offers high branched selectivity and enantioselectivity and occurs with complete atom economy. Diastereocontrolled reduction of the products provides β 2 -amino acids that possess contiguous stereocenters.

Topics & Concepts

ChemistryDiphosphinesIridiumEnantioselective synthesisMetalationCationic polymerizationArylAlkeneMedicinal chemistryCatalysisStereochemistrySelectivityCombinatorial chemistryAlkylOrganic chemistryCatalytic C–H Functionalization MethodsAsymmetric Hydrogenation and CatalysisCatalytic Cross-Coupling Reactions
An Aza-Enolate Strategy Enables Iridium-Catalyzed Enantioselective Hydroalkenylations of Minimally Polarized Alkenes en Route to Complex N-Aryl β<sup>2</sup>-Amino Acids | Litcius