Hydrogen Peroxide → Tert-butyl 4-(3-hydroxypropoxy)-4-methylpiperidine-1-carboxylate
Reaction equation
[CH2:1]([O:4][C:5]1([CH3:18])[CH2:10][CH2:9][N:8]([C:11]([O:13][C:14]([CH3:17])([CH3:16])[CH3:15])=[O:12])[CH2:7][CH2:6]1)[CH:2]=[CH2:3].B1C2CCCC1CCC2.[OH-:28].[Na+].OO>C1COCC1>[OH:28][CH2:3][CH2:2][CH2:1][O:4][C:5]1([CH3:18])[CH2:6][CH2:7][N:8]([C:11]([O:13][C:14]([CH3:17])([CH3:16])[CH3:15])=[O:12])[CH2:9][CH2:10]1Participants
Procedure
To a solution of tert-butyl 4-(allyloxy)-4-methylpiperidine-1-carboxylate (8.4 g, 32.9 mmol) in THF (200 mL) at room temp was added 0.5 M solution of 9-BBN (132 mL, 65.8 mmol) and the resulting mixture was stirred at room temp for 16 h. Mixture was then cooled in an ice bath and 1N NaOH (164 mL, 164 mmol) followed by 30% H2O2 (30.2 mL, 296 mmol) were added and the mixture was stirred for 1 h. Mixture was then extracted with ethyl acetate (250 mL), washed with water (100 mL), brine (100 mL), dried (Na2SO4), filtered and concentrated. The residue was then purified by Biotage (5-80% EtOAc/Hexane) to afford tert-butyl 4-(3-hydroxypropoxy)-4-methylpiperidine-1-carboxylate (6.4 g, 23.41 mmol, 71.2% yield) as colorless oil. 1H NMR (500 MHz, CDCl3) δ 3.84-3.79 (m, 2H), 3.74 (dt, J=13.4, 3.7 Hz, 2H), 3.57 (t, J=5.6 Hz, 2H), 3.19-3.06 (m, 2H), 1.85 (quin, J=5.6 Hz, 2H), 1.75 (d, J=13.1 Hz, 2H), 1.48 (s, 9H), 1.47-1.41 (m, 2H), 1.21 (s, 3H). LCMS (M+Na)=296.7.
Workup
- temperatureMixture was then cooled in an ice bath
- additionwere added
- stirringthe mixture was stirred for 1 h
- extractionMixture was then extracted with ethyl acetate (250 mL)
- washwashed with water (100 mL), brine (100 mL)
- dry with materialdried (Na2SO4)
- filtrationfiltered
- concentrationconcentrated
- customThe residue was then purified by Biotage (5-80% EtOAc/Hexane)
Sources & evidence
- ORD record
- ord-e537d1305521403ab7f649041deca836
- Source dataset
- uspto-grants-2016_03
- Patent number
- US09273067B2
Reaction notes
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