International audienceSynthetic applications of cyclobutanones other than ring expansion and fragmentation reactions are rare. Herein, highly efficient diastereo- and enantioselective organocatalytic Michael additions of 2-substituted cyclobutanone derivatives to nitroalkenes are reported allowing the stereocontrolled creation of " all-carbon " quaternary centers. The approach relies on both the use of Brønsted base/hydrogen-bond donor bifunctional organocatalysts, and importantly, the specific stabilization and activation of cyclobutanone with a secondary amide moiety. The reaction was found to nicely accommodate a broad scope of substrates, allowing the control of up to three contiguous stereogenic centers. This work has opened new synthetic opportunities

The first organocatalytic enantio- and diastereoselective conjugate addition of α-ketoamides to nitroalkenes has been achieved using a bifunctional amino thiourea catalyst. In this new approach, the substrate amide proton plays a critical role in the formation of the Michael anti-adducts in high yields and high stereoselectivities. To illustrate the high synthetic potential of this methodology, the diastereo- and enantioselective synthesis of a hexasubstituted cyclohexane via a Michael-Michael-Henry cascade reaction is described.

This article concentrates on the versatile nucleophilic reactivity of 1,2-dicarbonyl compounds in various asymmetric transformations. Although underexploited in comparison to their 1,3-dicarbonyl homologues, the presence of adjacent multiple reactive centres allows the selection of specific activation modes for enhancing the reactivity of these important ambident pronucleophiles. They can be involved in selective formation of C-C, C-O or C-N bonds leading to various optically active targets in the acyclic and cyclic series including three- to seven-membered ring systems. Recent contributions in the field of biochemical, organometallic and organic catalytic transformations as well as some relevant stoichiometric approaches are discussed from synthetic and mechanistic point of views highlighting some important stereochemical issues.