Triphenylphosphine → 5-nitro-6-((S)-2-imidazol-1-yl-1-phenyl-ethoxy)-3,4-dihydro-2H-naphthalen-1-one

HRID 496407Notes

Reaction equation

HRID 496407 reaction equation
[OH:1][C:2]1[C:3]([N+:13]([O-:15])=[O:14])=[C:4]2[C:9](=[CH:10][CH:11]=1)[C:8](=[O:12])[CH2:7][CH2:6][CH2:5]2.[N:16]1([CH2:21][C@@H:22]([C:24]2[CH:29]=[CH:28][CH:27]=[CH:26][CH:25]=2)O)[CH:20]=[CH:19][N:18]=[CH:17]1.C1(P(C2C=CC=CC=2)C2C=CC=CC=2)C=CC=CC=1.CCOC(/N=N/C(OCC)=O)=O>C1COCC1.CO.C(Cl)Cl>[N+:13]([C:3]1[C:2]([O:1][C@@H:22]([C:24]2[CH:29]=[CH:28][CH:27]=[CH:26][CH:25]=2)[CH2:21][N:16]2[CH:20]=[CH:19][N:18]=[CH:17]2)=[CH:11][CH:10]=[C:9]2[C:4]=1[CH2:5][CH2:6][CH2:7][C:8]2=[O:12])([O-:15])=[O:14]

Participants

7

Reactant 4

HCID 11776TriphenylphosphineHCID 707108(R)-2-Imidazol-1-yl-1-phenyl-ethanolHCID 5462977Diethyl azodicarboxylateHCID 123928306-Hydroxy-5-nitro-3,4-dihydronaphthalen-1(2H)-one

Product 1

HCID 600298755-nitro-6-((S)-2-imidazol-1-yl-1-phenyl-ethoxy)-3,4-dihydro-2H-naphthalen-1-oneYield 80.2%

Reagents, catalysts & solvents 2

HCID 8028TetrahydrofuranSolventHCID 21226129Dichloromethane methanolSolvent

Procedure

To a solution of 6-hydroxy-5-nitro-1-tetralone (2.09 g, 10.1 mmol) in dry THF (50 mL) was added (R)-2-imidazol-1-yl-1-phenyl-ethanol (2.28 g, 12.1 mmol) followed by triphenylphosphine (3.18 g, 12.1 mmol). After approximately 10 min, diethylazodicarboxylate (1.9 mL, 12.1 mmol) was added slowly. The reaction became homogenous within 2 min. The reaction was allowed to stir at RT overnight. The reaction mixture was concentrated under reduced pressure and the residue was triturated with Et2O to remove some of the phospine by-products. The residue was dissolved in EtOAc and washed with H2O, saturated aqueous NaHCO3 and brine, dried over MgSO4, and concentrated to give a foam/oil. Purification by chromatography (SiO2, 10 to 20% acetone/Cl2Cl2 then 5% MeOH/CH2Cl2) afforded the title compound as a light brown foam (3.06 g, 8.1 mmol, 80%). The structure was confirmed by NMR and mass spectrometry. MS m/z 378 (M++H).

Workup

  1. waitThe reaction became homogenous within 2 min
  2. concentrationThe reaction mixture was concentrated under reduced pressure
  3. customthe residue was triturated with Et2O
  4. customto remove some of the phospine by-products
  5. dissolutionThe residue was dissolved in EtOAc
  6. washwashed with H2O, saturated aqueous NaHCO3 and brine
  7. dry with materialdried over MgSO4
  8. concentrationconcentrated
  9. customto give a foam/oil
  10. customPurification by chromatography (SiO2, 10 to 20% acetone/Cl2Cl2

Sources & evidence

ORD record
ord-24f9a1b636ea4b21b0ed361ea093fddf
Source dataset
uspto-grants-2005_09
Patent number
US06943183B2

Reaction notes

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