Formic Acid → (3S)-3-hydroxy-3-phenylpropanenitrile

HRID 2120003Notes

Reaction equation

HRID 2120003 reaction equation
[C:1]([CH2:9][C:10]#[N:11])(=[O:8])[C:2]1[CH:7]=[CH:6][CH:5]=[CH:4][CH:3]=1.C(N(CC)CC)C.C(O)=O>CC1C=CC(C(C)C)=CC=1.CC1C=CC(S([N-][C@H]([C@@H](N)C2C=CC=CC=2)C2C=CC=CC=2)(=O)=O)=CC=1.[Cl-].[Ru+2].O>[OH:8][C@H:1]([C:2]1[CH:7]=[CH:6][CH:5]=[CH:4][CH:3]=1)[CH2:9][C:10]#[N:11]

Participants

6

Reactant 3

HCID 284Formic AcidHCID 8471TriethylamineHCID 64799Benzoylacetonitrile

Product 1

HCID 11084031(3S)-3-hydroxy-3-phenylpropanenitrileYield 86.2%

Reagents, catalysts & solvents 2

HCID 11549108RuCl[(S,S)-Tsdpen](p-cymene)CatalystHCID 962WaterSolvent

Procedure

A 50 ml Schlenk flask was charged with 7.26 g (50.0 mmol) of benzoylacetonitrile, 18.1 ml (130 mmol) of triethylamine, 5.8 ml (155 mmol) of formic acid, and 31.8 mg (0.05 mmol, S/C=1000) of RuCl[(S,S)-Tsdpen](p-cymene) under an atmosphere of argon, and stirring was carried out at 30° C. for 24 hours. The solution was poured into water and extracted with ether, the organic layer was washed with saturated brine and then dried with anhydrous sodium sulfate, and the solvent was distilled off under vacuum. The crude product so obtained was distilled under vacuum (0.4 mmHg, 145° C.) to give 6.34 g (yield 86%, 1H-NMR) of (S)-3-hydroxy-3-phenylpropanenitrile. When this was analyzed using a CHIRALCEL OJ column (manufactured by Daicel Chemical Industries, Ltd., eluant; n-hexane:2-propanol=20:1) it was found that the optical purity was 98% ee.

Workup

  1. extractionextracted with ether
  2. washthe organic layer was washed with saturated brine
  3. dry with materialdried with anhydrous sodium sulfate
  4. distillationthe solvent was distilled off under vacuum
  5. customThe crude product so obtained
  6. distillationwas distilled under vacuum (0.4 mmHg, 145° C.)

Sources & evidence

ORD record
ord-b2006526c28c4d6490a25c3d5f2d6793
Source dataset
uspto-grants-2004_02
Patent number
US06686505B2

Reaction notes

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