Palladium-catalyzed asymmetric umpolung allylation of imines with allylic alcohols

A palladium-catalyzed asymmetric umpolung allylation reaction of imines with allylic alcohols has been developed. In the presence of chiral spiro phosphoramidite ligand 4, the allylation was accomplished with high yields and good enantioselectivities. The use of highly stable and easily available allylic alcohols instead of allylic metal reagents facilitated the preparation of chiral homoallylic amines.

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N-(1-Phenylbut-3-enyl)-4-methylbenzenesulfonamideC17H19NO2SEe = 68%[α]D15=-60.6 (c 0.5, CH2Cl2)Source of chirality: asymmetric synthesisAbsolute configuration: unknown

N-(1-(4-Fluorophenyl)but-3-enyl)-4-methylbenzenesulfonamideC17H18FNO2SEe = 77%[α]D19=+55.2 (c 0.5, CH2Cl2)Source of chirality: asymmetric synthesisAbsolute configuration: unknown

N-(1-(4-Chlorophenyl)but-3-enyl)-4-methylbenzenesulfonamideC17H18ClNO2SEe = 80%[α]D18=-80.4 (c 0.5, CH2Cl2)Source of chirality: asymmetric synthesisAbsolute configuration: unknown

N-(1-(4-Trifluoromethylphenyl)but-3-enyl)-4-methylbenzenesulfonamideC18H18F3NO2SEe = 79%[α]D18=-58.6 (c 0.5, CH2Cl2)Source of chirality: asymmetric synthesisAbsolute configuration: unknown

N-(1-(4-Methylphenyl)but-3-enyl)-4-methylbenzenesulfonamideC18H21NO2SEe = 69%[α]D19=+66.4 (c 0.5, CH2Cl2)Source of chirality: asymmetric synthesisAbsolute configuration: unknown

N-(1-(4-Methoxyphenyl)but-3-enyl)-4-methylbenzenesulfonamideC18H21NO3SEe = 74%[α]D18=-69.6 (c 0.5, CH2Cl2)Source of chirality: asymmetric synthesisAbsolute configuration: unknown

N-(1-(3-Chlorophenyl)but-3-enyl)-4-methylbenzenesulfonamideC17H18ClNO2SEe = 58%[α]D18=-45.4 (c 1.8, CH2Cl2)Source of chirality: asymmetric synthesisAbsolute configuration: unknown

N-(1-m-Tolylbut-3-enyl)-4-methyl-benzenesulfonamideC18H21NO2SEe = 46%[α]D18=-36.5 (c 1.75, CH2Cl2)Source of chirality: asymmetric synthesisAbsolute configuration: unknown

N-(1-(2-Chlorophenyl)but-3-enyl)-4-methylbenzenesulfonamideC17H18ClNO2SEe = 65%[α]D18=-44.2 (c 0.5, CH2Cl2)Source of chirality: asymmetric synthesisAbsolute configuration: unknown

N-(1-(2-Methoxyphenyl)but-3-enyl)-4-methylbenzenesulfonamideC18H21NO3SEe = 64%[α]D18=-26.0 (c 1.6, CH2Cl2)Source of chirality: asymmetric synthesisAbsolute configuration: unknown

(S)-N-(1-(Furan-2-yl)but-3-enyl)-4-methylbenzenesulfonamideC15H17NO3SEe = 75%[α]D15=-43.6 (c 0.5, CHCl3)Source of chirality: asymmetric synthesisAbsolute configuration: (S)

(E)-4-Methyl-N-(1-phenylhexa-1,5-diene-3-yl)benzenesulfonamideC19H21NO2SEe = 76%[α]D18=-91.2 (c 1.2, CH2Cl2)Source of chirality: asymmetric synthesisAbsolute configuration: unknown

N-(1-Cyclohexylbut-3-enyl)-4-methylbenzenesulfonamideC17H25NO2SEe = 77%[α]D19=+8.8 (c 0.5, CH2Cl2)Source of chirality: asymmetric synthesisAbsolute configuration: unknown

N-(1-Phenylbut-3-enyl)-4-(trifluoromethyl)benzenesulfonamideC17H16F3NO2SEe = 60%[α]D15=+24.6 (c 0.98, CH2Cl2)Source of chirality: asymmetric synthesisAbsolute configuration: unknown

N-(1-Phenylbut-3-enyl)-4-methoxybenzenesulfonamideC17H19NO3SEe = 67%[α]D15=+44.5 (c 1.58, CH2Cl2)Source of chirality: asymmetric synthesisAbsolute configuration: unknown

(S)-N-(1-Phenylbut-3-enyl)benzenesulfonamideC16H17NO2SEe = 63%[α]D15=-43.4 (c 0.5, CHCl3)Source of chirality: asymmetric synthesisAbsolute configuration: (S)

syn-N-(2-Methyl-1-phenylbut-3-enyl)-4-methylbenzenesulfonamideC18H21NO2SEe = 69%[α]D19=+55.4 (c 0.5, CH2Cl2)Source of chirality: asymmetric synthesisAbsolute configuration: unknown

syn-N-(1,2-Diphenylbut-3-enyl)-4-methylbenzenesulfonamideC23H23NO2SEe = 65%[α]D19=+15.6 (c 0.5, CH2Cl2)Source of chirality: asymmetric synthesisAbsolute configuration: unknown

N-(3-Methyl-1-phenylbut-3-enyl)-4-methylbenzenesulfonamideC18H21NO2SEe = 81%[α]D19=+95 (c 0.5, CH2Cl2)Source of chirality: asymmetric synthesisAbsolute configuration: unknown