Hydrochloric Acid → 2-tert-Butoxycarbonylamino-3-(4-bromophenylsulfanyl)-propanoic acid methyl ester

HRID 900377Notes

Reaction equation

HRID 900377 reaction equation
[CH3:1][O:2][C:3](=[O:18])[CH:4]([NH:10][C:11]([O:13][C:14]([CH3:17])([CH3:16])[CH3:15])=[O:12])[CH2:5][S:6]([CH3:9])(=O)=O.[Br:19][C:20]1[CH:25]=[CH:24]C(S)=[CH:22][CH:21]=1.C([O-])([O-])=O.[Cs+].[Cs+].Cl>CN(C=O)C.C(OCC)(=O)C>[CH3:1][O:2][C:3](=[O:18])[CH:4]([NH:10][C:11]([O:13][C:14]([CH3:17])([CH3:16])[CH3:15])=[O:12])[CH2:5][S:6][C:9]1[CH:24]=[CH:25][C:20]([Br:19])=[CH:21][CH:22]=1

Participants

7

Reactant 4

HCID 313Hydrochloric AcidHCID 10796Cesium carbonateHCID 660494-BromothiophenolHCID 866053502-tert-Butoxycarbonylamino-3-methylsulfonylpropanoic acid methyl ester

Product 1

HCID 596962102-tert-Butoxycarbonylamino-3-(4-bromophenylsulfanyl)-propanoic acid methyl esterYield 76%

Reagents, catalysts & solvents 2

HCID 6228DimethylformamideSolventHCID 8857Ethyl AcetateSolvent

Procedure

Solution of 2-tert-Butoxycarbonylamino-3-methylsulfonylpropanoic acid methyl ester (0.86 g, 2.89 mmol) and 4-bromobenzenthiol (0.56 g, 2.89 mmol) in DMF (10 mL) was cooled to at 0° C. and treated with Cs2CO3 (1.1 g, 3.2 mmol). After stirring at room temperature for 2 h, the reaction was acidified with 5% HCl (15 mL) and diluted with ethyl acetate (25 mL). After separation, the aqueous layer was extracted with ethyl acetate (3×15 mL) and the combined organic layers were washed with sat. aq NaCl, dried over MgSO4, filtered, and concentrated. Purification by flash column chromatography (5% ethyl acetate in heptane) gave the desired product (857 mg, 76%) as a white solid. 1H NMR (CDCl3), δ 7.40 (d, J=9 Hz, 2H), 7.27 (d, J=9, 2H), 5.30 (d, J=7 Hz, 1H), 4.56 (m, 1H), 3.59 (s, 3H), 3.35 (ddd, J=7, 7, 12 Hz, 2H), 1.47 (s, 9H).

Workup

  1. customAfter separation
  2. extractionthe aqueous layer was extracted with ethyl acetate (3×15 mL)
  3. washthe combined organic layers were washed with sat. aq NaCl
  4. dry with materialdried over MgSO4
  5. filtrationfiltered
  6. concentrationconcentrated
  7. customPurification by flash column chromatography (5% ethyl acetate in heptane)

Sources & evidence

ORD record
ord-4f951ec0e6ce48979f1726b0be7a24e8
Source dataset
uspto-grants-2008_04
Patent number
US07358248B2

Reaction notes

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