N-Heterocyclic carbene-catalyzed (NHC) three-component domino reactions: highly stereoselective synthesis of functionalized acyclic epsilon-ketoesters

A novel NHC-catalyzed three-component domino strategy to access high functionalized cis-epsilon-ketoesters with excellent yields (up to 98%) and high stereoselectivities (up to 20 : 1) is documented. The title domino reactions are atom economical and work on a broad range of substrates. The relative stereochemistry could be explained by a cascade crossed-benzoin/oxy-Cope rearrangement/esterification process. The thus-obtained products are of potential synthetic value in the drug research and combinatorial chemistry.