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Visible-Light-Activated Asymmetric β‑C–H Functionalization of Acceptor-Substituted Ketones with 1,2-Dicarbonyl Compounds

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posted on 21.11.2017, 17:10 authored by Jiajia Ma, Anthony R. Rosales, Xiaoqiang Huang, Klaus Harms, Radostan Riedel, Olaf Wiest, Eric Meggers
We report a visible-light-activated asymmetric β-C­(sp3)–H functionalization of 2-acyl imidazoles and 2-acylpyridines with 1,2-dicarbonyl compounds (typically α-ketoesters) catalyzed by a tailored stereogenic-at-rhodium Lewis acid catalyst. The C–C bond formation products are obtained in high yields (up to 99%) and with excellent stereoselectivities (up to >20:1 dr and up to >99% ee). Experimental and computational studies support a mechanism in which a photoactivated Rh-enolate transfers a single electron to the 1,2-dicarbonyl compound followed by proton transfer and a subsequent stereocontrolled radical–radical recombination.