tert-butyl N-(4-oxocyclohexyl)carbamate → cis-4-(Boc-amino)-1-methylcyclohexanol

HRID 724264Notes

Reaction equation

HRID 724264 reaction equation
[CH3:1][Mg]Cl.[O:4]=[C:5]1[CH2:10][CH2:9][CH:8]([NH:11][C:12](=[O:18])[O:13][C:14]([CH3:17])([CH3:16])[CH3:15])[CH2:7][CH2:6]1>O1CCCC1>[OH:4][C:5]1([CH3:1])[CH2:6][CH2:7][CH:8]([NH:11][C:12](=[O:18])[O:13][C:14]([CH3:15])([CH3:17])[CH3:16])[CH2:9][CH2:10]1

Participants

4

Reactant 2

HCID 1512535tert-butyl N-(4-oxocyclohexyl)carbamateHCID 178418332HCID 178418332, compound

Product 1

HCID 21877240cis-4-(Boc-amino)-1-methylcyclohexanolYield 5.3%

Reagents, catalysts & solvents 1

HCID 8028TetrahydrofuranSolvent

Procedure

A solution of methyl magnesium chloride (3M in tetrahydrofuran, 57 ml, 171 mmol) was added to a solution of tert-butyl 4-oxocyclohexylcarbamate (12 g, 56 mmol) (WO9613262) in tetrahydrofuran (240 ml) at −78° C. The mixture was allowed to warm to ambient temperature and was stirred for 18 h. The mixture was quenched by the addition of saturated ammonium chloride solution (100 ml) and the volatile solvents were removed under reduced pressure. The residue was taken up in water (200 ml) and dichloromethane (400 ml) and solid citric acid was added until the layers separated. The organic phase was washed with saturated sodium bicarbonate solution, water, brine, dried over MgSO4, and the solvent removed under reduced pressure to give a gum which was purified by flash column chromatography using ethyl acetate:cyclohexane (20:80 to 80:20) as eluant to give the less polar diastereoisomer of tert-butyl 4-hydroxy-4-methylcyclohexylcarbamate (680 mg) as a white solid.

Workup

  1. customThe mixture was quenched by the addition of saturated ammonium chloride solution (100 ml)
  2. customthe volatile solvents were removed under reduced pressure
  3. additiondichloromethane (400 ml) and solid citric acid was added until the layers
  4. customseparated
  5. washThe organic phase was washed with saturated sodium bicarbonate solution, water, brine
  6. dry with materialdried over MgSO4
  7. customthe solvent removed under reduced pressure
  8. customto give a gum which
  9. customwas purified by flash column chromatography

Sources & evidence

ORD record
ord-ea3a1244d70b4198990e5bb6cb9f2451
Source dataset
uspto-grants-2006_11
Patent number
US07141586B2

Reaction notes

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