Oxidative Umpolung α-Alkylation of Ketones
O. Svetlana Shneider, Evgeni Pisarevsky, Peter Fristrup and Alex M. Szpilman*
*Schulich Faculty of Chemistry, Technion-Israel Institute of Technology, 3200008, Haifa, Israel, Email: Szpilmantx.technion.ac.il
O. S. Shneider, E. Pisarevsky, P. Fristrup, A. M. Szpilman, Org. Lett., 2015, 17, 282-285.
DOI: 10.1021/ol503384c (free Supporting Information)
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A hypervalent iodine mediated α-alkylative umpolung reaction of carbonyl compounds with dialkylzinc as the alkyl source is applicable to a broad range of ketones including 1,3-dicarbonyl compounds and regular ketones via their lithium enolates. The α-alkylated carbonyl products are formed in very good yield. Meticulous analysis, NMR studies, trapping and crossover experiments, and computational studies suggest an ionic mechanism.
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