Visible-Light-Promoted Enantioselective α-Amidation of Aldehydes by Harnessing Organo-Iron Dual Catalysis
Soumyadip Hore, Jiwoo Jeong, Dongwook Kim, Sukbok Chang
Abstract
The strategic integration of organocatalysis with transition-metal catalysis to achieve otherwise unattainable stereoselective transformations may serve as a powerful synthetic tool. Herein, we present a synthetically versatile α-amidation of aldehydes by leveraging dual iron and chiral enamine catalysis in an enantioselective manner (up to >99:1 er). Experimental and computational studies have led us to propose a new mechanistic platform, wherein visible-light-promoted LMCT generates [Fe(II)Cl 3 – ], which effectively activates dioxazolones to form an iron-acylnitrenoid radical that inserts into chiral enamine intermediates.
Topics & Concepts
ChemistryEnantioselective synthesisEnamineOrganocatalysisCatalysisStereoselectivityCombinatorial chemistrySynergistic catalysisDual (grammatical number)Transition metalNanotechnologyOrganic chemistryArtMaterials scienceLiteratureCatalytic C–H Functionalization MethodsSynthesis and Catalytic ReactionsChemical Synthesis and Analysis