1,2-Acyl transfer reaction for the construction of multiple carbonyl-functionalized architecture by Sm(II)-induced tandem formation and breaking of cyclopropanol

An efficient 1,2-acyl group migration reaction based on contiguous formation and breaking tactics of 1-oxycyclopropane-2-carboxylate as an intermediate is developed. Thus, the reduction of 2-cyclohexenones, bearing gem-acyl/alkoxycarbonyl groups at the C4 position, with Sm(II) reagent leads to 2-acyl-4-oxycyclohexanecarboxylates via cyclization followed by retro-aldol cleavage of the resulting donor/acceptor cyclopropane. Mechanistic insights and the scope of the reaction are described.