title: Oxidative umpolung α-alkylation of ketones.
abstract: We disclose a hypervalent iodine mediated α-alkylative umpolung reaction of carbonyl compounds with dialkylzinc as the alkyl source. The reaction is applicable to all common classes of ketones including 1,3-dicarbonyl compounds and regular ketones via their lithium enolates. The α-alkylated carbonyl products are formed in up to 93% yield. An ionic mechanism is inferred based on meticulous analysis, NMR studies, trapping and crossover experiments, and computational studies.
authors.affiliation: Schulich Faculty of Chemistry, Technion-Israel Institute of Technology , 3200008, Haifa, Israel.
authors.forename: O Svetlana
authors.initials: OS
authors.lastname: Shneider
authors.forename: Evgeni
authors.initials: E
authors.lastname: Pisarevsky
authors.forename: Peter
authors.initials: P
authors.lastname: Fristrup
authors.forename: Alex M
authors.initials: AM
authors.lastname: Szpilman