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)

A series of cyclopropane-based bisoxazolines were synthesized from (R)- and (S)-amino alcohols, and applied to copper-catalyzed enantioselective nitroaldol reactions between nitromethane and various aldehydes. The reactions generated β-hydroxy nitroalkanes in high yields (97%) and with good enantioselectivities (up to 87% ee). The effects of the oxazoline stereocenters constructed in the Henry reactions were also studied.(1R,2S)-1,2-Bis[4(S)-isopropyloxazolin-2-yl]-3,3-dimethylcyclopropaneC17H28N2O2[α]D20=-131.3 (c 1.6, CHCl3)Source of chirality: (S)-valinol(1R,2S)-1,2-Bis [4(S)-tert-butyloxazolin-2-yl]-3,3-dimethylcyclopropaneC19H32N2O2[α]D20=-135.8 (c 2.1, CHCl3)Source of chirality: (S)-tert-leucinol(1R,2S)-1,2-Bis[4(S)-benzyloxazolin-2-yl]-3,3-dimethylcyclopropaneC25H28N2O2[α]D20=-56.5 (c 0.78, CHCl3)Source of chirality: (S)-phenylalaninol(1R,2S)-1,2-Bis[4(R)-phenyloxazolin-2-yl]-3,3-dimethylcyclopropaneC23H24N2O2[α]D25=+160.2 (c 1.5, CHCl3)Source of chirality: (R)-phenylglycinol(1R,2S)-1,2-Bis[4(S)-phenyloxazolin-2-yl]-3,3-dimethylcyclopropaneC23H24N2O2[α]D20=-152.3 (c 2.0, CHCl3)Source of chirality: (S)-phenylglycinolAbsolute configuration: (1R,2S)(1R,2S)-1,2-Bis[4(R)-phenyloxazolin-2-yl]-3,3-dimethylcyclopropaneC17H28N2O2[α]D25=+126.5 (c 2.4, CHCl3)Source of chirality: (R)-phenylglycinolAbsolute configuration: (1R,2S)