p-Aminoacetophenone → 4-Amino-alpha-methylbenzenemethanol

HRID 1855130Notes

Reaction equation

[NH2:1][C:2]1[CH:7]=[CH:6][C:5]([C:8](=[O:10])[CH3:9])=[CH:4][CH:3]=1.C(=O)([O-])[O-].[Na+].[Na+]>O1CCCC1.C1C=CC(P(C2C=CC=CC=2)C2C=CC=CC=2)=CC=1.C1C=CC(P(C2C=CC=CC=2)C2C=CC=CC=2)=CC=1.C1C=CC(P(C2C=CC=CC=2)C2C=CC=CC=2)=CC=1.[Cl-].[Cl-].[Ru+2].[Fe]>[NH2:1][C:2]1[CH:7]=[CH:6][C:5]([CH:8]([OH:10])[CH3:9])=[CH:4][CH:3]=1

Participants

Conditions

Temperature: 65 °C

Procedure

Tris(triphenylphosphine)ruthenium(II) chloride (1.9 mg, 2 μmol, 0.5 mol %) and a chiral ligand (M=Fe, R=t-Bu, Ar=3,5-(CF3)2C6H3—, 1.3 μmol, 0.33 mol %) were dissolved in tetrahydrofuran (3 mL) under nitrogen atmosphere, and then heated and stirred for 1 h at 65° C. After the mixture was cooled to room temperature, p-amino-acetophenone (0.4 mmol), tetrahydrofuran (2 mL) and an aqueous solution of sodium carbonate (0.4 mL, 0.2 M) were added thereto. Thereafter, the reaction system was placed in an autoclave, and stirred for 48 h under H2 (20 atm) at 0° C. The solvent was removed under reduced pressure, and the resultants were separated by column chromatography (silica gel column; eluent:ethyl acetate/petroleum ether=1/1). Accordingly, pure 1-(p-aminophenyl)ethanol was obtained and the ee value (ee=97%) was measured by GC analysis.

Workup

temperatureheated
temperatureAfter the mixture was cooled to room temperature
stirringstirred for 48 h under H2 (20 atm) at 0° C
customThe solvent was removed under reduced pressure
customthe resultants were separated by column chromatography (silica gel column; eluent:ethyl acetate/petroleum ether=1/1)

Sources & evidence

ORD record: ord-6157bc2378d142439e9752a7b2b93e7f
Source dataset: uspto-grants-2015_02
DOI: 10.6084/m9.figshare.5104873.v1
Patent number: US08962852B2

Reaction notes

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