An efficient route for the allylation of arylaldehydes to give enantiopure homoallylic alcohols

An efficient asymmetric synthesis of homoallylic alcohols is described by the allylation of carbonyl compounds using organocatalysts as chiral directors in the presence of tin metal. The effect of chiral environment is also studied on the allylation reactions. This method allows us to obtain two different enantiomers of homoallylic alcohol in the presence of the corresponding chiral compound. The protocol is applied to various aldehydes to obtain high yields and excellent enantioselectivities for the corresponding homoallylic alcohols.

Graphical abstractFigure optionsDownload full-size imageDownload as PowerPoint slide

(S)-1-Acetyl-N-tosylpyrrolidine-2-carboxamideC14H18N2O4S[α]D = −125.7 (c 0.5, ethyl acetate)Source of Chirality: Chiral synthesisAbsolute configuration: (S)

(S)-N-(4-Fluorophenyl)-1-tosylpyrrolidine-2-carboxamideC18H19FN2O3S[α]D = −115.2 (c 0.5, ethyl acetate)Source of Chirality: Chiral synthesisAbsolute configuration: (S)

(S)-1-Acetylpyrrolidine-2-carboxylic 4-methylbenzenesulfonic anhydrideC14H17NO5S[α]D27=-94.6 (c 0.5, ethyl acetate)Source of Chirality: Chiral synthesisAbsolute configuration: (S)

(S)-4-Fluorophenyl N-tosylpyrrolidine-2-carboxylateC18H18FNO4S[α]D27=-102.9 (c 0.5, ethyl acetate)Source of Chirality: Chiral synthesis.Absolute configuration: (S)

(S)-1-Acetylpyrrolidine-2-carboxylic 4-nitrobenzenesulfonic anhydrideC13H14N2O7S[α]D27=-76.4 (c 0.5, ethyl acetate)Source of Chirality: Chiral synthesisAbsolute configuration: (S)

(S)-p-Tolyl 1-tosylpyrrolidine-2-carboxylateC19H21NO4S[α]D27=+119.9 (c 1.5, ethyl acetate)Source of Chirality: Chiral ResolutionAbsolute configuration: (S)

(S)-1-(4-Nitrophenyl)but-3-en-1-olC10H11NO3[α]D27=-13.1 (c 3.5, benzene)Source of Chirality: Asymmetric synthesisAbsolute configuration: (S)

(S)-1-(2-Nitrophenyl)but-3-en-1-olC10H11NO3[α]D27=-36.9 (c 2.9, benzene)Source of Chirality: Asymmetric synthesis.Absolute configuration: (S)

(S)-1-(4-Chlorophenyl)but-3-en-1-olC10H11ClO[α]D27 = -15.6 (c 2.4, benzene)Source of Chirality: Asymmetric synthesisAbsolute configuration: (S)

(S)-1-(2-Chlorophenyl) but-3-en-1-olC10H11ClO[α]D27=-21.3 (c 1.8, CHCl3)Source of Chirality: Asymmetric synthesisAbsolute configuration: (S)

(S)-1-(4-Fluorophenyl) but-3-en-1-olC10H11FO[α]D27=-21.5 (c 2.0, benzene)Source of Chirality: Asymmetric synthesisAbsolute configuration: (S)

(S)-1-(4-Bromophenyl)but-3-en-1-olC10H11BrO[α]D27=-12.5 (c 3.5, benzene)Source of Chirality: Asymmetric synthesisAbsolute configuration: (S)

(S)-1-Phenylbut-3-en-1-olC10H12O[α]D27=-22.0 (c 2.0, benzene)Source of Chirality: Asymmetric synthesisAbsolute configuration: (S)

(S)-1-(2-Methoxyphenyl)but-3-en-1-olC11H14O2[α]D27=-44.6 (c 2.0, benzene)Source of Chirality: Asymmetric synthesisAbsolute configuration: (S)

(S)-1-(4-Methoxyphenyl)but-3-en-1-olC11H14O2[α]D27=-15.6 (c 1.6, benzene)Source of Chirality: Asymmetric synthesis.Absolute configuration: (S)

(S)-1-p-Tolylbut-3-en-1-olC11H14O[α]D27=-15.3 (c 2.0, benzene)Source of Chirality: Asymmetric synthesis.Absolute configuration: (S)

(S)-1-(Naphthalen-1-yl) but-3-en-1-olC14H14O[α]D27=-99.0 (c 1.0, benzene)Source of Chirality: Asymmetric synthesisAbsolute configuration: (S)

(S)-1-(3-Pyridyl) but-3-en-1-olC9H11NO[α]D27=-40.0 (c 0.5, CH2Cl2)Source of Chirality: Asymmetric synthesis.Absolute configuration: (S)

(S)-1-(Thiophen-2-yl)but-3-en-1-olC8H10OS[α]D27=-8.3 (c 0.5, CH2Cl2)Source of Chirality: Asymmetric synthesisAbsolute configuration: (S)

(S)-1-(Furan-2-yl)but-3-en-1-olC8H10O2[α]D27=-32.7 (c 0.5, CH2Cl2)Source of Chirality: Asymmetric synthesisAbsolute configuration: (S)

(R)-1-(4-Nitrophenyl)but-3-en-1-olC10H11NO3[α]D27=+13.4 (c 3.5, benzene)Source of Chirality: Asymmetric synthesis.Absolute configuration: (R)

(R)-1-(2-Nitrophenyl)but-3-en-1-olC10H11NO3[α]D27=+37.4 (c 2.9, benzene)Source of Chirality: Asymmetric synthesis.Absolute configuration: (R)

(R)-1-(4-Chlorophenyl)but-3-en-1-olC10H11ClO[α]D27=+15.4 (c 2.4, benzene)Source of Chirality: Asymmetric synthesisAbsolute configuration: (R)

(R)-1-(2-Chlorophenyl)but-3-en-1-olC10H11ClO[α]D27=+20.9 (c 1.8, CHCl3)Source of Chirality: Asymmetric synthesisAbsolute configuration: (R)

(R)-1-(4-Fluorophenyl)but-3-en-1-olC10H11FO[α]D27=+21.2 (c 2.0, benzene)Source of Chirality: Asymmetric synthesis.Absolute configuration: (R)

(R)-1-(4-Bromophenyl)but-3-en-1-olC10H11BrO[α]D27=+12.9 (c 3.5, benzene)Source of Chirality: Asymmteric synthesisAbsolute configuration: (R)

(R)-1-Phenylbut-3-en-1-olC10H12O[α]D27=+22.1 (c 2.0, benzene)Source of Chirality: Asymmetric synthesisAbsolute configuration: (R)

(R)-1-(2-Methoxyphenyl)but-3-en-1-olC11H14O2[α]D27 = +44.1 (c 2.0, benzene)Source of Chirality: Asymmetric synthesisAbsolute configuration: (R)

(R)-1-(4-Methoxyphenyl)but-3-en-1-olC11H14O2[α]D27=+15.1 (c 1.6, benzene)Source of Chirality: Asymmetric synthesis.Absolute configuration: (R)

(R)-1-p-tolylbut-3-en-1-olC11H14O[α]D27=+15.1 (c 2.0, benzene)Source of Chirality: Asymmetric synthesis.Absolute configuration: (R)

(R)-1-(Naphthalen-1-yl)but-3-en-1-olC14H14O[α]D27=+98.6 (c 1.0, benzene)Source of Chirality: Asymmetric synthesisAbsolute configuration: (R)

(R)-1-(3-Pyridyl)but-3-en-1-olC9H11NO[α]D27=+39.8 (c 0.5, CH2Cl2)Source of Chirality: Asymmetric synthesis.Absolute configuration: (R)

(R)-1-(Thiophen-2-yl)but-3-en-1-olC8H10OS[α]D27=+8.0 (c 0.5, CH2Cl2)Source of Chirality: Asymmetric synthesisAbsolute configuration: (R)

(R)-1-(Furan-2-yl)but-3-en-1-olC8H10O2[α]D27=-32.7 (c 0.5, CH2Cl2)Source of Chirality: Asymmetric synthesisAbsolute configuration: (R)