Copper-catalyzed asymmetric propargylic amination of propargylic acetates with amines using BICMAP

The copper-catalyzed asymmetric propargylic amination of propargylic acetates 1 with amines 2 using BICMAP as a chiral ligand gave the desired products 3 in good yields and with moderate to high enantioselectivities (up to 90% ee).

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(S)-(+)-N-Methyl-N-(1-phenyl-2-propynyl)anilineC16H15Nee = 87% from HPLC[α]D20=+6.2 (c 0.27, CHCl3)Souce of chirality: Asymmetric synthesisAbsolute configuration: (S)

(S)-(−)-N-Methyl-N-[1-(4-methylphenyl)-2-propynyl]anilineC17H17Nee = 77% from HPLC[α]D20=-1.4 (c 0.50, CHCl3)Souce of chirality: Asymmetric synthesisAbsolute configuration: (S)

(S)-(−)-N-Methyl-N-[1-(4-chlorophenyl)-2-propynyl]anilineC16H14ClNee = 87% from HPLC[α]D20=-12.1 (c 0.49, CHCl3)Souce of chirality: Asymmetric synthesisAbsolute configuration: (S)

(S)-(−)-N-Methyl-N-[1-(4-methoxyphenyl)-2-propynyl]anilineC17H17NOee = 37% from HPLC[α]D20=-8.0 (c 0.25, CHCl3)Souce of chirality: Asymmetric synthesisAbsolute configuration: (S)

(S)-(+)-N-Methyl-N-[1-(2-methylphenyl)-2-propynyl]anilineC17H17Nee = 81% from HPLC[α]D20=+41.2 (c 0.25, CHCl3)Souce of chirality: Asymmetric synthesisAbsolute configuration: (S)

(S)-(−)-N-Methyl-N-[1-(naphthalen-2-yl)-2-propynyl]anilineC20H17Nee = 72% from HPLC[α]D20=-7.1 (c 0.81, CHCl3)Souce of chirality: Asymmetric synthesisAbsolute configuration: (S)

(S)-(+)-N-Methyl-N-(1-phenyl-2-propynyl)-p-methylanilineC17H17Nee = 83% from HPLC[α]D20=+16.8 (c 0.25, CHCl3)Souce of chirality: Asymmetric synthesisAbsolute configuration: (S)

(S)-(+)-N-Methyl-N-(1-phenyl-2-propynyl)-p-methoxyanilineC17H17NOee = 79% from HPLC[α]D20=+12.7 (c 0.52, CHCl3)Souce of chirality: Asymmetric synthesisAbsolute configuration: (S)

(S)-(+)-N-Methyl-N-(1-phenyl-2-propynyl)-p-chloroanilineC16H14ClNee = 90% from HPLC[α]D20=+3.3 (c 0.28, CHCl3)Souce of chirality: Asymmetric synthesisAbsolute configuration: (S)

(S)-(−)-N-Ethyl-N-(1-phenyl-2-propynyl)-p-chloroanilineC17H16ClNee = 88% from HPLC[α]D20=-27.1 (c 0.22, CHCl3)Souce of chirality: Asymmetric synthesisAbsolute configuration: (S)

(S)-(−)-N-Ethyl-N-(1-phenyl-2-propynyl)anilineC17H17Nee = 82% from HPLC[α]D20=-13.8 (c 0.31, CHCl3)Souce of chirality: Asymmetric synthesisAbsolute configuration: (S)

(S)-(+)-N-(1-Phenyl-2-propynyl)anilineC15H13Nee = 44% from HPLC[α]D20=+33.3 (c 0.27, CHCl3)Souce of chirality: Asymmetric synthesisAbsolute configuration: (S)

(S)-(+)-N-Methyl-N-(1-phenyl-2-propynyl)indolineC17H15Nee = 70% from HPLC[α]D20=+54.3 (c 0.23, CHCl3)Souce of chirality: Asymmetric synthesisAbsolute configuration: (S)