Chelating 2-azanorbornyl derivatives as effective nitrogen–nitrogen and nitrogen–chalcogen donating ligands in palladium-catalyzed asymmetric allylic alkylation

New chiral 2-azanorbornane derivatives were prepared and used as (N,S)-, (N,Se)-, and (N,N)-donating ligands in a palladium-catalyzed asymmetric allylic alkylation, giving up to 95% ee and 92% yield.

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(−)-(1S,3R,4R)-2-Benzyl-3-phenylsulfanylmethyl-2-azabicyclo[2.2.1]heptaneC20H23NS[α]D20=-13.1 (c 1.56, CH2Cl2) >95% eeSource of chirality: chiral substrateAbsolute configuration: (S,R,R) (by chemical correlation)

(−)-(1S,3R,4R)-2-[(S)-1-Phenylethyl]-3-phenylsulfanylmethyl-2-azabicyclo[2.2.1]heptaneC21H25NS[α]D20=-5.1 (c 1.47, CH2Cl2) >95% eeSource of chirality: chiral substratesAbsolute configuration: (S,R,R,S) (by chemical correlation)

(−)-(1S,3R,4R)-2-Benzyl-3-phenylselenalylmethyl-2-azabicyclo[2.2.1]heptaneC20H23NSe[α]D20=-32.5 (c 0.80, CH2Cl2) >95% eeSource of chirality: chiral substrateAbsolute configuration: (S,R,R) (by chemical correlation)

(−)-(1S,3R,4R)-2-[(S)-1-Phenylethyl]-3-phenylselenalylmethyl-2-azabicyclo[2.2.1]heptaneC21H25NSe[α]D20=-80.3 (c 0.66, CH2Cl2) >95% eeSource of chirality: chiral substratesAbsolute configuration: (S,R,R,S) (by chemical correlation)

(−)-Bis-3-{(1S,3R,4R)-2-[(S)-1-Phenylethyl]-2-azabicyclo[2.2.1]heptane}methyl disulfideC30H40N2S2[α]D20=-126.6 (c 0.30, CH2Cl2) >95% eeSource of chirality: chiral substratesAbsolute configuration: (S,R,R,S) (by chemical correlation)

(−)-(1S,3R,4R)-2-[(S)-1-Phenylethyl]-3-[(S)-1-phenylethylimine]methyl-2-azabicyclo[2.2.1]heptaneC23H28N2[α]D20=-2.5 (c 1.58, CH2Cl2) >95% e.e.Source of chirality: chiral substratesAbsolute configuration: (S,R,R,S,S) (by chemical correlation)

(+)-(1S,3R,4R)-2-[(S)-1-Phenylethyl]-3-[(R)-1-phenylethylimine]methyl-2-azabicyclo[2.2.1]heptaneC23H28N2[α]D20=+52.9 (c 0.44, CH2Cl2) >95% eeSource of chirality: chiral substratesAbsolute configuration: (S,R,R,S,R) (by chemical correlation)

(+)-(1S,3R,4R)-2-[(S)-1-Phenylethyl]-3-(2-dithiane)-2-azabicyclo[2,2,1]heptaneC18H25NS2[α]D20=+18.4 (c 0.68, CH2Cl2, >95% ee)Source of chirality: chiral substrateAbsolute configuration: (S,R,R,S) (by chemical correlation)

(+)-(1S,3R,4R)-2-[(S)-1-Phenylethyl]-3-(2-dithiolate)-2-azabicyclo[2.2.1]heptaneC17H23NS2[α]D20=+3.4 (c 0.74, CH2Cl2) >95% e.e.Source of chirality: chiral substrateAbsolute configuration: (S,R,R,S) (by chemical correlation)