Optically active palladium-catalyzed asymmetric amination of aryl halide

The asymmetric amination of aryl halides with racemic amines was examined in the presence of a transition metal complex having a chiral ligand. The yield and enantioselectivity of the products were strongly influenced by the kind of base, reaction temperature, solvent, and the additive. The best result was obtained from the reaction of 2-iodoanisole with 1-(1-naphthyl)ethylamine in the presence of sodium methoxide and 18-crown-6 by Pd–Tol–BINAP to afford the product in 70% yield with 80% ee.

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(S)-4-Phenyl-N-(1-phenylethyl)anilineC20H19NEe = 21%[α]D25=-11.9 (c 0.5, CHCl3)Source of chirality: asymmetric synthesisAbsolute configuration: (S)

(S)-4-Methyl-N-(1-phenylethyl)anilineC15H17NEe = 20%[α]D25=+26 (c 0.5, CHCl3)Source of chirality: asymmetric synthesisAbsolute configuration: (S)

(S)-3-Methyl-N-(1-phenylethyl)anilineC15H17NEe = 16%[α]D25=+16 (c 0.5, CHCl3)Source of chirality: asymmetric synthesisAbsolute configuration: (S)

(S)-2-Methyl-N-(1-phenylethyl)anilineC15H17NEe = 25%[α]D25=+14 (c 0.5, CHCl3)Source of chirality: asymmetric synthesisAbsolute configuration: (S)

(R)-4-Methoxy-N-(1-phenylethyl)anilineC15H17NOEe = 21%[α]D25=+6.0 (c 0.3, CHCl3)Source of chirality: asymmetric synthesisAbsolute configuration: (R)

(R)-3-Methoxy-N-(1-phenylethyl)anilineC15H17NOEe = 19%[α]D25=+8.0 (c 0.5, CHCl3)Source of chirality: asymmetric synthesisAbsolute configuration: (R)

(S)-2-Methoxy-N-(1-phenylethyl)anilineC15H17NOEe = 30%[α]D25=+14.0(c 0.5, CHCl3)Source of chirality: asymmetric synthesisAbsolute configuration: (S)

(S)-N-(1-(1-Naphthyl)ethyl)-4-phenylanilineC24H21NEe = 37%[α]D25=+86 (c 0.5, CHCl3)Source of chirality: asymmetric synthesisAbsolute configuration: (S)

(R)-2-Methyl-N-(1-(1-naphthyl)ethyl)anilineC19H19NEe = 100%[α]D25=+226 (c 0.5, CHCl3)Source of chirality: asymmetric synthesisAbsolute configuration: (R)

(R)-N-(1-(1-Naphthyl)ethyl)anilineC18H17NEe = 75%[α]D25=+142 (c 0.5, CHCl3)Source of chirality: asymmetric synthesisAbsolute configuration: (R)

(S)-2-Methoxy-N-(1-(1-naphthyl)ethyl)anilineC19H19NEe = 80%[α]D25=+170 (c 0.3, CHCl3)Source of chirality: asymmetric synthesisAbsolute configuration: (S)