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

HRID 1499936Notes

Reaction equation

HRID 1499936 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.[C:19]([C:22]1[CH:29]=[C:28]([Cl:30])[C:25]([C:26]#[N:27])=[C:24]([CH:31]=[CH2:32])[C:23]=1[O:33][CH2:34][CH3:35])(=[O:21])[CH3:20].C(=O)([O-:38])N>O.C(#N)C.[Os](=O)(=O)(=O)=O>[C:19]([C:22]1[C:23]([O:33][CH2:34][CH3:35])=[C:24]([CH:31]([OH:38])[CH2:32][NH:9][C:10](=[O:16])[O:11][C:12]([CH3:15])([CH3:14])[CH3:13])[C:25]([C:26]#[N:27])=[C:28]([Cl:30])[CH:29]=1)(=[O:21])[CH3:20]

Participants

7

Reactant 3

HCID 276CarbamateHCID 23655003tert-Butyl (4-Chlorobenzoyl)oxycarbamateHCID 866778524-Acetyl-6-chloro-3-ethoxy-2-vinylbenzonitrile

Product 1

HCID 86677853tert-Butyl [2-(3-acetyl-5-chloro-6-cyano-2-ethoxyphenyl)-2-hydroxyethyl]carbamate

Reagents, catalysts & solvents 3

HCID 30318Osmium TetroxideCatalystHCID 962WaterSolvent2×HCID 6342AcetonitrileSolvent2×

Procedure

0.2 M Osmium tetraoxide in water (0.5 mL) was added to a solution of tert-butyl [(4-chlorobenzoyl)oxy]carbamate (Ref. Lawrence Harris, J. Org. Chem., 2011, 76, 358-372). (0.91 g, 3.3 mmol) in acetonitrile (10 mL) and stirred for 10 minutes. 4-Acetyl-6-chloro-3-ethoxy-2-vinylbenzonitrile (0.56 g, 2.2 mmol) as a solution in acetonitrile (10 mL) was added to the carbamate solution followed by the addition of water (2 mL) and the reaction was stirred for 3 hours at room temperature. The reaction was quenched with saturated 10 M dipotassium disulfite in water (12 mL) and stirred for 5 minutes. Water was added and the reaction mixture was extracted with ethyl acetate. The extracts were washed with saturated sodium bicarbonate solution, brine and dried over sodium sulfate, filtered and evaporated. Purification on silica gel using ethyl acetate in hexane (0-100%) gave the desired compound as a racemic mixture, 610 mg, 72%. LCMS calculated for C18H24ClN2O5 (M+H)+: m/z=383.1; found: 383.1. 1H NMR (400 MHz, DMSO-d6): δ 7.62 (s, 1 H), 7.03 (br s, 1 H), 5.68 (br s, 1 H), 3.96 (m, 1 H), 3.69 (m, 1 H), 3.31 (m, 1 H), 3.19 (m, 1 H), 2.60 (s, 3 H), 1.30 (m, 12 H).

Workup

  1. customThe reaction was quenched with saturated 10 M dipotassium disulfite in water (12 mL)
  2. stirringstirred for 5 minutes
  3. additionWater was added
  4. extractionthe reaction mixture was extracted with ethyl acetate
  5. washThe extracts were washed with saturated sodium bicarbonate solution, brine
  6. dry with materialdried over sodium sulfate
  7. filtrationfiltered
  8. customevaporated
  9. customPurification on silica gel

Sources & evidence

ORD record
ord-d88372ec5c6244d5a8f97628dafe9795
Source dataset
uspto-grants-2015_12
Patent number
US09199982B2

Reaction notes

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