Triphenylphosphine → HCID 117634603, compound

HRID 878411Notes

Reaction equation

HRID 878411 reaction equation
CS(O[CH2:6][C@@H:7]([NH:11][C:12]([O:14][CH2:15][C:16]1[CH:21]=[CH:20][CH:19]=[CH:18][CH:17]=1)=[O:13])[CH2:8][O:9][CH3:10])(=O)=O.[N-:22]=[N+]=[N-].[Na+].C1(P(C2C=CC=CC=2)C2C=CC=CC=2)C=CC=CC=1>CN(C=O)C.[I-].C([N+](CCCC)(CCCC)CCCC)CCC.C(=O)(O)[O-].[Na+].O>[NH2:22][CH2:6][C@@H:7]([NH:11][C:12](=[O:13])[O:14][CH2:15][C:16]1[CH:21]=[CH:20][CH:19]=[CH:18][CH:17]=1)[CH2:8][O:9][CH3:10]

Participants

8

Reactant 3

HCID 11776TriphenylphosphineHCID 33557Sodium AzideHCID 89486854HCID 89486854, compound

Product 1

HCID 117634603HCID 117634603, compound

Reagents, catalysts & solvents 4

HCID 67553Tetrabutylammonium IodideCatalystHCID 962WaterSolventHCID 6228DimethylformamideSolventHCID 516892Sodium BicarbonateSolvent

Conditions

Temperature
80 °C

Procedure

To a solution of (2S)-2-{[(benzyloxy)carbonyl]amino}-3-methoxypropyl methanesulfonate (37.6 g, 0.118 mol) in DMF (400 mL) was added sodium azide (23.2 g, 0.178 mol) and tetrabutylammonium iodide (0.526 g, 1.42 mmol), and then the reaction mixture was heated to 80° C. After 3 hours, the reaction mixture was cooled to ambient temperature, diluted with saturated aqueous sodium bicarbonate, and extracted with ethyl acetate. The organic layer was dried over sodium sulfate and concentrated under reduced pressure. The residue was diluted with THF/water (250 mL/50 mL), and to this mixture was added triphenylphospine (36.7 g, 0.140 mol). After 2 hours, the reaction mixture was diluted with water and extracted with ethyl acetate (6×300 mL). The combined organic layers were dried over sodium sulfate and concentrated under reduced pressure. The residue was purified via chromatography on silica gel (3% methanol/DCM) to afford benzyl [(2R)-1-amino-3-methoxypropan-2-yl]carbamate. MS ESI calc'd. for C12H19N2O3 [M+H]+ 239. found 239. 1H NMR (400 MHz, CDCl3) δ 7.46-7.39 (m, 5H), 5.86 (d, J=7.2 Hz, 1H), 5.12-5.05 (m, 2H), 3.92 (bs, 1H), 3.55-3.49 (m, 2H), 3.34 (s, 3H), 2.93 (d, J=5.6 Hz, 2H), 1.91 (s, 2H).

Workup

  1. temperaturethe reaction mixture was cooled to ambient temperature
  2. extractionextracted with ethyl acetate
  3. dry with materialThe organic layer was dried over sodium sulfate
  4. concentrationconcentrated under reduced pressure
  5. additionThe residue was diluted with THF/water (250 mL/50 mL)
  6. waitAfter 2 hours
  7. extractionextracted with ethyl acetate (6×300 mL)
  8. dry with materialThe combined organic layers were dried over sodium sulfate
  9. concentrationconcentrated under reduced pressure
  10. customThe residue was purified via chromatography on silica gel (3% methanol/DCM)

Sources & evidence

ORD record
ord-a186a54d5557455c941b8751418f75c4
Source dataset
uspto-grants-2015_03
Patent number
US08987456B2

Reaction notes

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