Enantioselective Michael addition of anthrone to nitroalkenes catalyzed by bifunctional thiourea-tertiary amines

A highly bifunctional thiourea-tertiary amine-catalyzed enantioselective Michael addition reaction of anthrone to a wide variety of nitroalkenes has been developed, and the corresponding adducts were obtained smoothly in high yields (up to 97%) and good enantioselectivities (up to 94% ee).

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9-(2-Nitro-1-phenylethyl)anthracen-10(9H)-oneC22H17NO3Ee = 93%[α]D20=+25.4 (c 0.48, CHCl3)Source of chirality: asymmetric synthesisAbsolute configuration: unknown

9-(1-(4-Chlorophenyl)-2-nitroethyl)anthracen-10(9H)-oneC22H16ClNO3Ee = 93%[α]D20=+21.7 (c 0.40, CHCl3)Source of chirality: asymmetric synthesisAbsolute configuration: unknown

9-(1-(4-Methoxyphenyl)-2-nitroethyl)anthracen-10(9H)-oneC23H19NO4Ee = 86%[α]D20=+18.7 (c 0.74, CHCl3)Source of chirality: asymmetric synthesisAbsolute configuration: unknown

9-(2-Nitro-1-p-tolylethyl)anthracen-10(9H)-oneC23H19NO3Ee = 85%[α]D20=+25.4 (c 0.62, CHCl3)Source of chirality: asymmetric synthesisAbsolute configuration: unknown

9-(2-Nitro-1-(4-nitrophenyl)ethyl)anthracen-10(9H)-oneC22H16N2O5Ee = 80%[α]D20=+21.2 (c 0.42, CHCl3)Source of chirality: asymmetric synthesisAbsolute configuration: unknown

9-(1-(4-Bromophenyl)-2-nitroethyl)anthracen-10(9H)-oneC22H16BrNO3Ee = 91%[α]D20=+15.4 (c 0.54, CHCl3)Source of chirality: asymmetric synthesisAbsolute configuration: (S)

9-(1-(4-Fluorophenyl)-2-nitroethyl)anthracen-10(9H)-oneC22H16FNO3Ee = 94%[α]D20=+31.0 (c 0.46, CHCl3)Source of chirality: asymmetric synthesisAbsolute configuration: unknown

4-(2-Nitro-1-(9-oxo-9,10-dihydroanthracen-10-yl)ethyl)benzonitrileC23H16N2O3Ee = 91%[α]D20=+22.0 (c 0.62, CHCl3)Source of chirality: asymmetric synthesisAbsolute configuration: unknown

9-(1-(2-Bromophenyl)-2-nitroethyl)anthracen-10(9H)-oneC22H16BrNO3Ee = 83%[α]D20=+7.1 (c 0.74, CHCl3)Source of chirality: asymmetric synthesisAbsolute configuration: unknown

9-(1-(2-Methoxyphenyl)-2-nitroethyl)anthracen-10(9H)-oneC23H19NO4Ee = 89%[α]D20=-8.6 (c 0.88, CHCl3)Source of chirality: asymmetric synthesisAbsolute configuration: unknown

9-(2-Nitro-1-(2-nitrophenyl)ethyl)anthracen-10(9H)-oneC22H16N2O5Ee = 90%[α]D20=-4.0 (c 0.20, CHCl3)Source of chirality: asymmetric synthesisAbsolute configuration: unknown

9-(1-(2-Chlorophenyl)-2-nitroethyl)anthracen-10(9H)-oneC22H16ClNO3Ee = 84%[α]D20=-14.8 (c 0.54, CHCl3)Source of chirality: asymmetric synthesisAbsolute configuration: unknown

9-(2-Nitro-1-m-tolylethyl)anthracen-10(9H)-oneC23H19NO3Ee = 91%[α]D20=+33.2 (c 0.60, CHCl3)Source of chirality: asymmetric synthesisAbsolute configuration: unknown

9-(2-Nitro-1-(3-Nitrophenyl)ethyl)anthracen-10(9H)-oneC22H16N2O5Ee = 90%[α]D20=+38.1 (c 0.40, CHCl3)Source of chirality: asymmetric synthesisAbsolute configuration: unknown

9-(1-(3-Bromophenyl)-2-nitroethyl)anthracen-10(9H)-oneC22H16BrNO3Ee = 90%[α]D20=+31.0 (c 0.58, CHCl3)Source of chirality: asymmetric synthesisAbsolute configuration: unknown

9-(2-Nitro-1-(3-(trifluoromethyl)phenyl)ethyl)anthracen-10(9H)-oneC23H16F3NO3Ee = 91%[α]D20=+26.2 (c 0.44, CHCl3)Source of chirality: asymmetric synthesisAbsolute configuration: unknown

9-(1-(3-Fluorophenyl)-2-nitroethyl)anthracen-10(9H)-oneC22H16FNO3Ee = 90%[α]D20=+26.3 (c 0.58, CHCl3)Source of chirality: asymmetric synthesisAbsolute configuration: unknown

9-(1-(2,4-Dichlorophenyl)-2-nitroethyl)anthracen-10(9H)-oneC22H15Cl2NO3Ee = 81%[α]D20=-16.0 (c 0.22, CHCl3)Source of chirality: asymmetric synthesisAbsolute configuration: unknown

9-(1-(Furan-2-yl)-2-nitroethyl)anthracen-10(9H)-oneC20H15NO4Ee = 90%[α]D20=-2.3 (c 0.74, CHCl3)Source of chirality: asymmetric synthesisAbsolute configuration: unknown

9-(2-Nitro-1-(thiophen-2-yl)ethyl)anthracen-10(9H)-oneC20H15NO3SEe = 91%[α]D20=+17.3 (c 0.50, CHCl3)Source of chirality: asymmetric synthesisAbsolute configuration: unknown

9-(1-(Naphthalen-1-yl)-2-nitroethyl)anthracen-10(9H)-oneC26H19NO3Ee = 60%[α]D20=-36.0 (c 0.60, CHCl3)Source of chirality: asymmetric synthesisAbsolute configuration: unknown

9-(3-Methyl-1-nitrobutan-2-yl)anthracen-10(9H)-oneC19H19NO3Ee = 84%[α]D20=+34.1 (c 0.45, CHCl3)Source of chirality: asymmetric synthesisAbsolute configuration: unknown

9-(4-Methyl-1-nitropentan-2-yl)anthracen-10(9H)-oneC20H21NO3Ee = 86%[α]D20=+24.3 (c 0.64, CHCl3)Source of chirality: asymmetric synthesisAbsolute configuration: unknown

9-(1-Cyclohexyl-2-nitroethyl)anthracen-10(9H)-oneC22H23NO3Ee = 85%[α]D20=+61.0 (c 0.24, CHCl3)Source of chirality: asymmetric synthesisAbsolute configuration: unknown