Organocatalytic Enantioselective Intramolecular (Hetero)Michael Additions in Desymmetrization Processes

The organocatalytic enantioselective desymmetrization reaction by means of an intramolecular (hetero)Michael addition is a useful strategy for the creation of complex carbo‐ and heterocycles with the generation of multiple stereocenters in a very simple manner. The intramolecular addition of carbon, oxygen and nitrogen nucleophiles to prochiral substrates bearing electronically deficient olefins takes place in the presence of organocatalysts, such as chiral primary and secondary amines, NHCs, ureas, thioureas, and BINOL phosphoric acid derivatives, reaching high levels of diastereo‐ and enantioselectivity. The main bottleneck of this methodology is the design and synthesis of the starting materials, which compromises its application. To date, the majority of examples are related to the use of 1,4‐cyclohexanedione derivatives.