A series of diastereomerically pure Schiff base ligands based on [2.2]paracyclophane backbones were synthesized and separated. The new planar chiral [2.2]paracyclophane Schiff bases were used as ligands in Cu-catalyzed asymmetric Henry reactions with high yields and enantioselectivities.(Sp,S)-5-(1-(1-Hydroxy-3,3-dimethylbutan-2-ylimino)ethyl)-4-hydroxy-13-fluoro-[2.2]paracyclophaneC24H30FNO2[α]D20=+655.0 (c 0.10, CH2Cl2)Source of chirality: (S)-tert-leucinolAbsolute configuration: (Sp,S)(Rp,S)-5-(1-(1-Hydroxy-3,3-dimethylbutan-2-ylimino)ethyl)-4-hydroxy-13-fluoro-[2.2]paracyclophaneC24H30FNO2[α]D20=-280 (c 0.10, CH2Cl2)Source of chirality: (S)-tert-leucinolAbsolute configuration: (Rp,S)(Sp,S)-5-(1-(1-Hydroxy-3,3-dimethylbutan-2-ylimino)ethyl)-4-hydroxy-13-iodo-[2.2]paracyclophaneC24H30INO2[α]D20=+756.0 (c 0.1, CH2Cl2)Source of chirality: (S)-tert-leucinolAbsolute configuration: (Sp,S)(Rp,S)-5-(1-(1-Hydroxy-3,3-dimethylbutan-2-ylimino)ethyl)-4-hydroxy-13-iodo-[2.2]paracyclophaneC24H30INO2[α]D20=-431.8 (c 0.1, CH2Cl2)Source of chirality: (S)-tert-leucinolAbsolute configuration: (Rp,S)(Sp,S)-5-(1-(1-Hydroxy-3,3-dimethylbutan-2-ylimino)ethyl)-4-hydroxy-13-methoxy-[2.2]paracyclophaneC25H33NO3[α]D20=+964.0 (c 0.1, CH2Cl2)Source of chirality: (S)-tert-leucinolAbsolute configuration: (Sp,S)(Rp,S)-5-(1-(1-Hydroxy-3,3-dimethylbutan-2-ylimino)ethyl)-4-hydroxy-13-methoxy-[2.2]paracyclophaneC25H33NO3[α]D20=-613.1 (c 0.1, CH2Cl2)Source of chirality: (S)-tert-leucinolAbsolute configuration: (Rp,S)(Rp,S)-5-(1-(1-Hydroxy-3,3-dimethylbutan-2-ylimino)ethyl)-4-hydroxy-13-(2,3-dimethoxyphenyl)-[2.2]paracyclophaneC32H39NO4[α]D20=+434.1 (c 0.1, CH2Cl2)Source of chirality: (S)-tert-leucinolAbsolute configuration: (Rp,S)

A series of chiral N,N′-dialkyl-1,2-cyclohexanediamine derivatives were designed, synthesized, and applied as ligands in asymmetric copper(II)-catalyzed Henry reactions. The catalysts based on such ligands and copper(II) acetate were found to promote asymmetric Henry reactions between aromatic/aliphatic aldehydes and nitromethane efficiently, and could provide the corresponding β-nitroalcohols in very good yields and with enantioselectivities of up to 93.6%.(1R,2R)-N1,N2-Diisopropylcyclohexane-1,2-diamineC12N26N2[α]D25=-25.8 (c 0.47, H2O)Source of chirality: The precursorAbsolute configuration: (1R,2R)(1R,2R)-N1,N2-Dibutylcyclohexane-1,2-diamineC14N30N2[α]D25=-56.9 (c 0.5, H2O)Source of chirality: The precursorAbsolute configuration: (1R,2R)(1R,2R)-N1,N2-Diisobutylcyclohexane-1,2-diamineC14N30N2[α]D25=-78.3 (c 0.5, H2O)Source of chirality: The precursorAbsolute configuration: (1R,2R)(1R,2R)-N1,N2-Dipentylcyclohexane-1,2-diamineC16N34N2[α]D25=-54.5 (c 0.5, H2O)Source of chirality: The precursorAbsolute configuration: (1R,2R)(1R,2R)-N1,N2-Diisopentylcyclohexane-1,2-diamineC16N34N2[α]D25=-53.8 (c 0.5, H2O)Source of chirality: The precursorAbsolute configuration: (1R,2R)(1R,2R)-N1,N2-Dineopentylcyclohexane-1,2-diamineC16N34N2[α]D25=-70.6 (c 0.4, H2O)Source of chirality: The precursorAbsolute configuration: (1R,2R)(1R,2R)-N1,N2-Didodecylcyclohexane-1,2-diamineC30N62N2[α]D25=-31.0 (c 0.6, MeOH)Source of chirality: The precursorAbsolute configuration: (1R,2R)(1R,2R)-N1,N2-Di-(2-butyl) cyclohexane-1,2-diamineC14N30N2[α]D25=-71.4 (c 0.5, H2O)Source of chirality: The precursorAbsolute configuration: (1R,2R)(1R,2R)-N1,N2-Di(2-pentanyl)cyclohexane-1,2-diamineC16N34N2[α]D25=-82.3 (c 0.5, H2O)Source of chirality: The precursorAbsolute configuration: (1R,2R)(1R,2R)-N1,N2-Di(2-hexanyl)cyclohexane-1,2-diamineC18N38N2[α]D25=-67.2 (c 0.6, H2O)Source of chirality: The precursorAbsolute configuration: (1R,2R)(1R,2R)-N1,N2-Di(3-pentanyl)cyclohexane-1,2-diamineC16N34N2[α]D25=-80.1 (c 0.5, H2O)Source of chirality: The precursorAbsolute configuration: (1R,2R)(1R,2R)-N1,N2-Bis(4-methylpentan-2-yl)cyclohexane-1,2-diamineC18N38N2[α]D25=-69.8 (c 0.5, H2O)Source of chirality: The precursorAbsolute configuration: (1R,2R)(1R,2R)-N1,N2-Bis(5-methylhexan-2-yl)cyclohexane-1,2-diamineC20N42N2[α]D25=-70.6 (c 0.5, H2O)Source of chirality: The precursorAbsolute configuration: (1R,2R)(1R,2R)-N1,N2-Bis(3,5,5-trimethylhexyl)cyclohexane-1,2-diamineC24N50N2[α]D25=-37.8 (c 0.5, H2O)Source of chirality: The precursorAbsolute configuration: (1R,2R)