Reaction Control in the Organocatalytic Asymmetric One‐Pot, Three‐Component Reaction of Aldehydes, Diethyl α‐Aminomalonate and Nitroalkenes: Toward Diversity‐Oriented Synthesis

Same reactants, different products: Either the Michael addition or [3+2] dipolar cycloaddition products from a one-pot, three-component reaction of aldehydes, diethyl α-aminomalonate and nitroalkenes are selectively obtained in high enantioselectivities, catalyzed by a bifunctional urea–tertiary amine or monothiourea compound, respectively (see scheme, Ar=3,5-(CF3)2C6H3, Ar1=3,5-F2C6H3).