Light-Driven Enantioselective Carbene-Catalyzed Radical-Radical Coupling |
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Authors: | Seunghwan Byun Meemie U Hwang Henry R Wise Anna V Bay Paul H-Y Cheong Prof Karl A Scheidt |
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Institution: | 1. Department of Chemistry, Northwestern University, Silverman Hall, Evanston, IL 60208 USA;2. Department of Chemistry, Oregon State University, 153 Gilbert Hall, Corvallis, OR 97331 USA |
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Abstract: | An enantioselective carbene-catalyzed radical-radical coupling of acyl imidazoles and racemic Hantzsch esters is disclosed. This method involves the coupling of an N-heterocyclic carbene-derived ketyl radical and a secondary sp3-carbon radical and allows access to chiral α-aryl aliphatic ketones in moderate-to-good yields and enantioselectivities without any competitive epimerization. The utility of this protocol is highlighted by the late-stage functionalization of various pharmaceutical compounds and is further demonstrated by the transformation of the enantioenriched products to biologically relevant molecules. Computational investigations reveal the N-heterocyclic carbene controls the double-facial selectivity of the ketyl radical and the alkyl radicals, respectively. |
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Keywords: | Asymmetric Catalysis N-Heterocyclic Carbenes Organocatalysis Photoredox Catalysis Radicals |
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