Oxidative umpolung α-alkylation of ketones

Org Lett. 2015 Jan 16;17(2):282-5. doi: 10.1021/ol503384c. Epub 2015 Jan 6.

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.