| Article ID | Journal | Published Year | Pages | File Type |
|---|---|---|---|---|
| 1348492 | Tetrahedron: Asymmetry | 2006 | 8 Pages |
A highly enantioselective cyano-phosphorylation of aldehydes catalyzed by a YLi3tris(binaphthoxide) complex YLB 1 is described. The slow addition of diethyl cyanophosphonate 4 to aldehydes 5 in the presence of YLB 1 (10 mol %), H2O (30 mol %), tris(2,6-dimethoxyphenyl)phosphine oxide 3a (10 mol %), and BuLi (10 mol %) afforded cyanohydrin O-phosphates 6 in up to 98% yield and 97% ee. Mechanistic studies revealed that the addition of cyanide to aldehydes is irreversible and determines the enantioselectivity. The reaction mechanism is also discussed in detail.
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(R)-1-Cyano-1-phenylmethyl diethyl phosphateC12H16NO4Ee = 92% ee (R)[α]D22=+18.9 (c 1.2, CHCl3)Source of chirality: asymmetric synthesisAbsolute configuration: (R)
1-Cyano-1-(4-methylphenyl)methyl diethyl phosphateC13H18NO4PEe = 93% ee (R)[α]D23=+16.5 (c 1.4, CHCl3)Source of chirality: asymmetric synthesisAbsolute configuration: (R)
1-Cyano-1-(2-naphthyl)methyl diethyl phosphateC16H18NO4PEe = 81% ee (R)[α]D22=+10.8 (c 1, CHCl3)Source of chirality: asymmetric synthesisAbsolute configuration: (R)
1-Cyano-1-(1-naphthyl)methyl diethyl phosphateC16H18NO4PEe = 89% ee (R)[α]D23=+67.7 (c 1.1, CHCl3)Source of chirality: asymmetric synthesisAbsolute configuration: (R)
1-Cyanohexyl diethyl phosphateC11H22NO4PEe = 92% ee (R)[α]D24=+21.0 (c 0.9, CHCl3)Source of chirality: asymmetric synthesisAbsolute configuration: (R)
1-Cyano-3-phenylpropyl diethyl phosphateC14H20NO4PEe = 82% ee (R)[α]D24=+7.4 (c 1.2, CHCl3)Source of chirality: asymmetric synthesisAbsolute configuration: (R)
1-Cyano-2-methylpropyl diethyl phosphateC9H18NO4PEe = 96% ee (R)[α]D23=+23.9 (c 1.4, CHCl3)Source of chirality: asymmetric synthesisAbsolute configuration: (R)
1-Cyano-1-cyclohexylmethyl diethyl phosphateC12H22NO4PEe = 97% ee (R)[α]D23=+15.0 (c 1.2, CHCl3)Source of chirality: asymmetric synthesisAbsolute configuration: (R)
1-Cyano-2,2-dimethyl-3-phenylpropyl diethyl phosphateC16H24NO4PEe = 76% ee (R)[α]D24=+8.7 (c 1.5, CHCl3)Source of chirality: asymmetric synthesisAbsolute configuration: (R)
1-Cyano-3-phenyl-2-propen-1-yl diethyl phosphateC14H18NO4PEe = 24% ee (R)[α]D22=-6.6 (c 1, CHCl3)Source of chirality: asymmetric synthesisAbsolute configuration: (R)
