Hydrogen Peroxide → Tert-butyl 4-(3-hydroxypropoxy)-4-methylpiperidine-1-carboxylate

HRID 921139Notes

Reaction equation

HRID 921139 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]1

Participants

6

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

  1. temperatureMixture was then cooled in an ice bath
  2. additionwere added
  3. stirringthe mixture was stirred for 1 h
  4. extractionMixture was then extracted with ethyl acetate (250 mL)
  5. washwashed with water (100 mL), brine (100 mL)
  6. dry with materialdried (Na2SO4)
  7. filtrationfiltered
  8. concentrationconcentrated
  9. 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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