Lewis acid-catalyzed asymmetric reactions of β,γ-unsaturated 2-acyl imidazoles

The investigation of diverse reactivity of beta,gamma -unsaturated carbonyl compounds is of great value in asymmetric catalytic synthesis. Numerous enantioselective transformations have been well developed with beta,gamma -unsaturated carbonyl compounds as nucleophiles, however, few example were realized by utilizing them as not only nucleophiles but also electrophiles under a same catalytic system. Here we report a regioselective catalytic asymmetric tandem isomerization/alpha -Michael addition of beta,gamma -unsaturated 2-acyl imidazoles in the presence of chiral N,N-dioxide metal complexes, delivering a broad range of optically pure 1,5-dicarbonyl compounds with two vicinal tertiary carbon stereocenters in up to >99% ee under mild conditions. Meanwhile, stereodivergent synthesis is disclosed to yield all four stereoisomers of products. Control experiments suggest an isomerization process involved in the reaction and give an insight into the role of NEt3. In addition, Mannich reaction and sulfur-Michael addition of beta,gamma -unsaturated 2-acyl imidazoles proceed smoothly as well under the same catalytic system. p id=Par The investigation of reactivity of beta,gamma -unsaturated carbonyl compounds is of great synthetic value, especially in asymmetric transformations. Here, the authors report a catalytic asymmetric tandem isomerization/alpha -Michael addition of beta,gamma -unsaturated 2-acyl imidazoles in presence of chiral N,N ' -dioxide metal catalysts.