α-Alkoxy Ketones from the Nucleophilic Substitution on the Peroxide Bond of 3,3-Disubstituted 1,2-Dioxetanes by Enamines

Article abstract of DOI:10.1021/jo00035a025

The reaction of 1,2-dioxetanes with enamines as ?-nucleophiles was investigated. 3,3-Dibenzyl-1,2-dioxetane (1) was allowed to react with enamines 2a-c in methylene chloride to afford after hydrolysis the corresponding α-alkoxylated ketones 4a-c.Additionally, the reaction of the dimedone-derived enamine 3 with dioxetane 1 yielded the oxidized enamine adduct 5.Nucleophilic attack of the enamine β-carbon (S_N2 reactivity) on the sterically less hindered site of the dioxetane peroxide bond is proposed to constitute the initial step of the reaction.