Carbamate → tert-Butyl [2-(3-acetyl-5-chloro-2-methoxy-6-methylphenyl)-2-hydroxyethyl]carbamate

HRID 1499941Notes

Reaction equation

HRID 1499941 reaction equation
ClC1C=CC(C(O[NH:9][C:10](=[O:16])[O:11][C:12]([CH3:15])([CH3:14])[CH3:13])=O)=CC=1.[Cl:19][C:20]1[C:21]([CH3:33])=[C:22]([CH:31]=[CH2:32])[C:23]([O:29][CH3:30])=[C:24]([C:26](=[O:28])[CH3:27])[CH:25]=1.C(=O)([O-:36])N>O.C(#N)C.[Os](=O)(=O)(=O)=O>[C:26]([C:24]1[C:23]([O:29][CH3:30])=[C:22]([CH:31]([OH:36])[CH2:32][NH:9][C:10](=[O:16])[O:11][C:12]([CH3:15])([CH3:14])[CH3:13])[C:21]([CH3:33])=[C:20]([Cl:19])[CH:25]=1)(=[O:28])[CH3:27]

Participants

7

Reactant 3

HCID 276CarbamateHCID 23655003tert-Butyl (4-Chlorobenzoyl)oxycarbamateHCID 866777491-(5-Chloro-2-methoxy-4-methyl-3-vinylphenyl)ethanone

Product 1

HCID 86677857tert-Butyl [2-(3-acetyl-5-chloro-2-methoxy-6-methylphenyl)-2-hydroxyethyl]carbamate

Reagents, catalysts & solvents 3

HCID 30318Osmium TetroxideCatalystHCID 962WaterSolvent2×HCID 6342AcetonitrileSolvent2×

Procedure

0.2 M Osmium tetraoxide in water (1 mL) was added to a solution of tert-butyl [(4-chlorobenzoyl)oxy]carbamate (2.0 g, 7.2 mmol) (Ref Lawrence Harris, J. Org. Chem., 2011, 76, 358-372) in acetonitrile (22 mL) and stirred for 10 minutes. 1-(5-Chloro-2-methoxy-4-methyl-3-vinylphenyl)ethanone (1.1 g, 4.8 mmol) as a solution in acetonitrile (22 mL) was added to the carbamate solution followed by the addition of water (5 mL). The reaction was stirred for 3 hours at room temperature. The reaction was quenched with saturated 10 M dipotassium disulfite in water (25 mL) and stirred for 5 minutes. Water was added to the reaction and the mixture was extracted with ethyl acetate. The organic extracts were washed with saturated sodium bicarbonate solution, brine, dried over sodium sulfate and evaporated under reduced pressure. Purification on silica gel using ethyl acetate in hexane (0-100%) gave the desired compound as a racemic mixture, 1.2 g, 69%. LCMS calculated for C17H24ClNO5Na (M+Na)+: m/z=380.1; found: 380.1. 1H NMR (500 MHz, DMSO-d6): δ 7.48 (s, 1 H), 6.80 (m, 1 H), 5.50 (br s, 1 H), 5.20 (br s, 1 H), 3.83 (s, 3 H), 3.32 (m, 1 H), 3.22 (m, 1 H), 2.59 (s, 3 H), 2.55 (s, 3 H), 1.32 (s, 9 H).

Workup

  1. stirringThe reaction was stirred for 3 hours at room temperature
  2. customThe reaction was quenched with saturated 10 M dipotassium disulfite in water (25 mL)
  3. stirringstirred for 5 minutes
  4. additionWater was added to the reaction
  5. extractionthe mixture was extracted with ethyl acetate
  6. washThe organic extracts were washed with saturated sodium bicarbonate solution, brine
  7. dry with materialdried over sodium sulfate
  8. customevaporated under reduced pressure
  9. customPurification on silica gel

Sources & evidence

ORD record
ord-e6a30eb8354742cd88c7f166fd3683db
Source dataset
uspto-grants-2015_12
Patent number
US09199982B2

Reaction notes

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