Development of Asymmetric Reactions Using Diaminomethylenemalononitrile Organocatalysts

Our recent research results on a diaminomethylenemalononitrile (DMM) organocatalyst will be introduced. DMM organocatalysts efficiently promoted the asymmetric conjugate additions of some nucleophiles such as α-cyanoketones, α-angerica lactones, and β-keto esters to benzoyl acrylonitriles as Michael acceptor to afford the corresponding addition products in high yields with excellent enantioselectivities. We demonstrated that benzoyl acrylonitriles are good Michael acceptor for asymmetric reactions using organocatalysts. In addition, N,N-dibenzyl DMM organocatalysts efficiently promoted the asymmetric Henry reaction of trifluoromethyl enones with nitromethane and the asymmetric 5-exo selective bromolactonization of stilbene-type carboxylic acids, resulting in the corresponding 1,2-adducts and phthalide derivatives with high stereoselectivities. We demonstrated that the molecules bearing both DMM motif as hydrogen-bond donor and chiral amine are good organocatalysts for some valuable stereoselective reactions.