Triphenylphosphine → N-[2-Benzyloxy-5-(2-amino-(1R)-1-hydroxy-ethyl)-phenyl]-methanesulfonamide

HRID 2300205Notes

Reaction equation

HRID 2300205 reaction equation
[CH2:1]([O:8][C:9]1[CH:14]=[CH:13][C:12]([C@@H:15]([O:18][Si](CC)(CC)CC)[CH2:16]I)=[CH:11][C:10]=1[NH:26][S:27]([CH3:30])(=[O:29])=[O:28])[C:2]1[CH:7]=[CH:6][CH:5]=[CH:4][CH:3]=1.[N-:31]=[N+]=[N-].[Na+].C1(P(C2C=CC=CC=2)C2C=CC=CC=2)C=CC=CC=1>CN(C)P(N(C)C)(N(C)C)=O.C(OCC)C>[CH2:1]([O:8][C:9]1[CH:14]=[CH:13][C:12]([C@@H:15]([OH:18])[CH2:16][NH2:31])=[CH:11][C:10]=1[NH:26][S:27]([CH3:30])(=[O:29])=[O:28])[C:2]1[CH:7]=[CH:6][CH:5]=[CH:4][CH:3]=1

Participants

6

Reactant 3

HCID 11776TriphenylphosphineHCID 33557Sodium AzideHCID 54211801(R)-N-[2-benzyloxy-5-(2-iodo-1-triethylsilyloxyethyl)phenyl]methanesulfonamide

Product 1

HCID 69654885N-[2-Benzyloxy-5-(2-amino-(1R)-1-hydroxy-ethyl)-phenyl]-methanesulfonamide

Reagents, catalysts & solvents 2

HCID 3283Diethyl EtherSolventHCID 12679HexamethylphosphoramideSolvent

Conditions

Temperature
60 °C

Procedure

A mixture of N-{2-benzyloxy-5-(2-iodo-(1R)-1-[(triethylsilyl)oxy]-ethyl)-phenyl}-methanesulfonamide (EP 0 659 737) (4.48 g, 8 mmol) and sodium azide (0.65 g, 10 mmol) in 100 mL of hexamethylphosphoramide was stirred at 60° C. overnight. After cooling to room temperature the mixture was diluted with diethyl ether, washed with water, dried over Na2SO4 and concentrated under reduced pressure. The residue was dissolved in 200 mL of THF/H2O (10:1) and triphenylphosphine (2.62 g, 10 mmol) was added. After overnight stirring at room temperature, the solvents were removed and the residue was partitioned between ethyl acetate and water. The organic layers were combined and dried over MgSO4 and concentrated. The residue was redissolved in 100 mL of THF and tetrabutylammonium fluoride (10 mL, 1 M solution in THF) was added. The reaction was stirred for 2 hours then the solvent was removed in vacuo. The residue was purified by column chromatography on silica gel using triethylamine-methanol-methylene chloride (1:1:3) to give the title compound as a white solid; MS (ES) m/z: 337.4 (M++H).

Workup

  1. temperatureAfter cooling to room temperature the mixture
  2. washwashed with water
  3. dry with materialdried over Na2SO4
  4. concentrationconcentrated under reduced pressure
  5. dissolutionThe residue was dissolved in 200 mL of THF/H2O (10:1)
  6. stirringAfter overnight stirring at room temperature
  7. customthe solvents were removed
  8. customthe residue was partitioned between ethyl acetate and water
  9. dry with materialdried over MgSO4
  10. concentrationconcentrated
  11. dissolutionThe residue was redissolved in 100 mL of THF
  12. additiontetrabutylammonium fluoride (10 mL, 1 M solution in THF) was added
  13. stirringThe reaction was stirred for 2 hours
  14. customthe solvent was removed in vacuo
  15. customThe residue was purified by column chromatography on silica gel

Sources & evidence

ORD record
ord-5b614a92e5084ee4a9e9395711ade467
Source dataset
uspto-grants-2002_12
Patent number
US06498170B2

Reaction notes

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