Synthesis of densely substituted α,β,γ,δ-dienones via the Pd(II)-catalyzed allylation, H-migration, and aerobic oxidative δ-hydride elimination cascade.
A novel protocol for the highly stereoselective synthesis of E,E-α,β,γ,δ-unsaturated dicarbonyl compounds is presented. Starting from the readily available allylic alcohols and 1,3-diketones, an array of E,E-α,β,γ,δ-dienones can be efficiently synthesized in high yields via Pd-catalyzed dehydrative allylation, H-migration, and aerobic oxidative δ-hydride elimination cascade. In addition to the novel reaction mechanism, the use of 1:1 allylic alcohol and 1,3-diketone as reactant, 5 mol % of PdCl(2) as catalyst, and 1 atm of environmentally benign O(2) as oxidant, as well as the generation of only H(2)O byproduct, makes this protocol rapid, simple, atom-efficient, and clean.
Changchun Institute of Applied Chemistry, Chinese Academy of Sciences, 5625 Renmin Street, Changchun 130022, Jilin, PR China.
Feng-Quan
FQ
Yuan
Fu-She
FS
Han