4-(Tert-butyldimethylsilyloxy)-1-(2-fluoro-5-nitrophenyl)-2-methylenebutan-1-ol → 4-(Tert-butyldimethylsilyloxy)-1-(2-fluoro-5-nitrophenyl)-2-methylenebutan-1-one
Reaction equation
[Si:1]([O:8][CH2:9][CH2:10][C:11](=[CH2:24])[CH:12]([C:14]1[CH:19]=[C:18]([N+:20]([O-:22])=[O:21])[CH:17]=[CH:16][C:15]=1[F:23])[OH:13])([C:4]([CH3:7])([CH3:6])[CH3:5])([CH3:3])[CH3:2]>C(Cl)(Cl)Cl.[O-2].[O-2].[Mn+4]>[Si:1]([O:8][CH2:9][CH2:10][C:11](=[CH2:24])[C:12]([C:14]1[CH:19]=[C:18]([N+:20]([O-:22])=[O:21])[CH:17]=[CH:16][C:15]=1[F:23])=[O:13])([C:4]([CH3:7])([CH3:6])[CH3:5])([CH3:3])[CH3:2]Participants
4
Reactant 1
Product 1
Reagents, catalysts & solvents 2
Procedure
To a solution of 4-(tert-butyldimethylsilyloxy)-1-(2-fluoro-5-nitrophenyl)-2-methylenebutan-1-ol (0.94 g, 2.64 mmol) from step B in chloroform (88 mL) was added manganese dioxide (3.45 g, 39.7 mmol), and the reaction mixture was heated under reflux for 24 h. The reaction mixture was filtered through a pad of Celite, and the filtrate was evaporated in vacuo. The residue was purified by chromatography eluting with 5-10% ethyl acetate/hexanes to give the title compound as a colorless oil (0.77 g, 82% yield). Some unreacted starting material was also recovered. 1H NMR (500 MHz, CDCl3) δ 8.26 (1H, m), 7.35 (1H, m), 6.18 (1H, s), 5.76 (1H, s), 3.83 (2H, t, J=6.0 Hz), 2.72 (2H, t, J=6.0 Hz), 0.90 (9H, s), and 0.08 (6H, s).
Workup
- temperaturethe reaction mixture was heated
- temperatureunder reflux for 24 h
- filtrationThe reaction mixture was filtered through a pad of Celite
- customthe filtrate was evaporated in vacuo
- customThe residue was purified by chromatography
- washeluting with 5-10% ethyl acetate/hexanes
Sources & evidence
- ORD record
- ord-b6c369a7fa374a87b6d671e0f4467e4c
- Source dataset
- uspto-grants-2013_12
- Patent number
- US08598161B2
Reaction notes
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