Water → HCID 118054599, compound

HRID 595969Notes

Reaction equation

HRID 595969 reaction equation
CS(O[CH2:6][C@@H:7]([NH:16][C:17]([O:19][C:20]([CH3:23])([CH3:22])[CH3:21])=[O:18])[C:8]1[CH:13]=[C:12]([F:14])[CH:11]=[C:10]([Br:15])[CH:9]=1)(=O)=O.[N-:24]=[N+:25]=[N-:26].[Na+].O.CCOC(C)=O>CN(C=O)C.C(Cl)Cl.CCCCCCC>[N:24]([CH2:6][C@@H:7]([NH:16][C:17](=[O:18])[O:19][C:20]([CH3:23])([CH3:22])[CH3:21])[C:8]1[CH:13]=[C:12]([F:14])[CH:11]=[C:10]([Br:15])[CH:9]=1)=[N+:25]=[N-:26]

Participants

8

Reactant 4

HCID 962WaterHCID 8857Ethyl AcetateHCID 33557Sodium AzideHCID 118045962HCID 118045962, compound

Product 1

HCID 118054599HCID 118054599, compoundYield 83.1%

Reagents, catalysts & solvents 3

HCID 6228DimethylformamideSolventHCID 6344DichloromethaneSolventHCID 8900HeptaneSolvent

Conditions

Temperature
70 °C

Procedure

(S)-2-((tert-butoxycarbonyl)amino)-2-(3-bromo-5-fluorophenyl)ethyl methanesulfonate (5.92 g, 14.36 mmol) was dissolved in anhydrous DMF (60 mL). Sodium azide (2.80 g, 43.1 mmol) was added, and the reaction heated to 70° C. and maintained at this temperature for 2 h. After cooling, the reaction mixture was poured into water (100 mL) and extracted with EtOAc (3×80 mL). The combined organics were washed with water (50 mL) and brine (3×50 mL), dried (MgSO4), filtered and concentrated. Flash chromatography (AnaLogix, 80 g column, loaded in DCM, 0 to 40% EtOAc in heptane over 30 min) gave (S)-tert-butyl (2-azido-1-(3-bromo-5-fluorophenyl)ethyl)carbamate (4.29 g, 11.94 mmol, 83% yield) as a white solid. 1H NMR (500 MHz, DMSO-d6) δ ppm 7.73 (d, J=8.83 Hz, 1H), 7.48 (t, J=4.26 Hz, 2H), 7.29 (d, J=9.77 Hz, 1H), 4.80 (d, J=8.20 Hz, 1H), 3.47 (d, J=7.88 Hz, 2H), 1.44-1.38 (m, 9H), 1.36 (br. s., 1H).

Workup

  1. temperaturemaintained at this temperature for 2 h
  2. temperatureAfter cooling
  3. extractionextracted with EtOAc (3×80 mL)
  4. washThe combined organics were washed with water (50 mL) and brine (3×50 mL)
  5. dry with materialdried (MgSO4)
  6. filtrationfiltered
  7. concentrationconcentrated

Sources & evidence

ORD record
ord-511182188987479086a3dd8a6d2b079a
Source dataset
uspto-grants-2016_01
Patent number
US09242996B2

Reaction notes

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