The novel fluorous organocatalyst bearing a diaminomethylenemalononitrile motif is prepared. The fluorous organocatalyst efficiently promotes asymmetric conjugate additions of ketones to nitroalkenes and results in high yields of these addition products with excellent enantioselectivities under solvent-free conditions.Key words organocatalyst; fluorous; conjugate addition; solvent-free Chiral γ-nitro carbonyl compounds are significant synthons in organic and medicinal chemistry owing to their easy access to biologically active molecules.1-9) Among several synthetic methods to obtain enantiomer-enriched, γ-nitro carbonyl compounds, asymmetric conjugate addition of carbonyl compounds to nitroalkenes using organocatalysts is one of the most convenient and environmentally benign methodologies. [10][11][12][13][14][15][16][17] Organocatalysis between carbonyl compounds and nitro alkenes has been reported by several research groups; however, due to obstacles faced by most previously reported organocatalysis, such as high catalyst loading or long reaction times, the development of organocatalysts for highly efficient asymmetric conjugate additions of carbonyl compounds to nitroalkenes still remains an area of research interest. Thiourea organocatalysts, which are represented by Takemoto catalysts, are excellent catalysts and are applied to remarkably important asymmetric reactions.18-26) Good organocatalytic activity is seen when a thiourea motif functions as a double hydrogen-bond donor for a nucleophilic substrate. In addition, a squaramide motif as a further double hydrogen-bond donor was reported by Rawal and colleagues, and the squaramide organocatalyst effectively promotes the asymmetric conjugate additions of 1,3-diketones to nitroalkenes. 27) Since the Rawal's report, it has been reported that various organocatalysts with squaramide motifs are useful for several important asymmetric reactions. [28][29][30][31][32][33][34][35][36][37][38][39][40][41][42][43] We recently reported the diaminomethylenemalononitrile (DMM) motif as another type of double hydrogen-bond donor, and the DMM-type organocatalysts exhibited excellent asymmetric catalytic activity for several significant asymmetric reactions. [44][45][46][47][48][49][50] Organocatalyst 1 bearing a DMM motif and a cyclic secondary amine unit is a good catalyst for both asymmetric conjugate additions of cyclic ketones to nitroalkenes and direct aldol reactions of aromatic aldehydes with cyclic ketones under solvent-free conditions 45,48) (Fig. 1). On the contrary, asymmetric reactions using organocatalysts with fluorous tags have been reported by several research groups. Almost all of these reports utilize the benefits of fluorous molecules; the recycling of fluorous organocatalysts was achieved via the fluorous solid-phase extraction (FSPE) technique using fluorous silica gel. [73][74][75] We have also reported some fluorous organocatalysts and demonstrated their recyclability. [76][77][78][79][80] It was found that modifying original organocatalysts via add...