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Visible-Light-Activated Asymmetric β-C-H Functionalization of Acceptor-Substituted Ketones with 1,2-Dicarbonyl
Jiajia Ma1, Anthony R Rosales2, Xiaoqiang Huang1
1Fachbereich Chemie, Philipps-Universität Marburg , Hans-Meerwein-Strasse 4, 35043 Marburg, Germany.
Abstract:
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.
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