3-Acetylpyridine → alpha-Methyl-3-pyridinemethanol

HRID 1855140Notes

Reaction equation

[C:1]([C:4]1[CH:5]=[N:6][CH:7]=[CH:8][CH:9]=1)(=[O:3])[CH3:2].[O-]CC.[K+]>O1CCCC1.C(O)C.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]>[OH:3][CH:1]([C:4]1[CH:5]=[N:6][CH:7]=[CH:8][CH:9]=1)[CH3:2]

Participants

Conditions

Temperature: 65 °C

Procedure

Tris(triphenylphosphine)ruthenium(II) chloride (3.8 mg, 4 μmol, 1 mol %) and a chiral ligand (M=Ru, R=t-Bu, Ar=C6H5—, 2.6 μmol, 0.65 mol %) were dissolved in tetrahydrofuran (3 mL) under nitrogen atmosphere, and then heated and stirred for 2 h at 65° C. After the mixture was cooled to room temperature, 3-acetylpyridine (0.4 mmol), tetrahydrofuran (2 mL) and a solution of potassium ethoxide in ethanol (0.1 mL, 0.2M) were added thereto. Thereafter, the reaction system was placed in an autoclave, and stirred for 6 h under H2 (50 atm) at 25° 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 3-(1-hydroxyethyl)pyridine was obtained and the ee value (ee=93%) was measured by GC analysis.

Workup

temperatureheated
temperatureAfter the mixture was cooled to room temperature
stirringstirred for 6 h under H2 (50 atm) at 25° 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-82405c15c68f43518ff460b3a76fb426
Source dataset: uspto-grants-2015_02
DOI: 10.6084/m9.figshare.5104873.v1
Patent number: US08962852B2

Reaction notes

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