Sodium Sulfite → sodium (S)-2-(tert-butoxycarbonylamino)-4-(methylthio)butane-1-sulfonate

HRID 2040501Notes

Reaction equation

HRID 2040501 reaction equation
CS(O[CH2:6][C@@H:7]([NH:12][C:13]([O:15][C:16]([CH3:19])([CH3:18])[CH3:17])=[O:14])[CH2:8][CH2:9][S:10][CH3:11])(=O)=O.[S:20]([O-:23])([O-:22])=[O:21].[Na+:24].[Na+]>CCO.O>[C:16]([O:15][C:13]([NH:12][C@@H:7]([CH2:8][CH2:9][S:10][CH3:11])[CH2:6][S:20]([O-:23])(=[O:22])=[O:21])=[O:14])([CH3:17])([CH3:18])[CH3:19].[Na+:24]

Participants

5

Reactant 2

HCID 24437Sodium SulfiteHCID 10358225(S)-2-(tert-butoxycarbonylamino)-4-(methylthio)butyl methanesulfonate

Product 1

HCID 86656460sodium (S)-2-(tert-butoxycarbonylamino)-4-(methylthio)butane-1-sulfonateYield 37%

Reagents, catalysts & solvents 2

HCID 702EthanolSolventHCID 962WaterSolvent

Procedure

(S)-2-(tert-butoxycarbonylamino)-4-(methylthio)butyl methanesulfonate (1.1 g, 3.51 mmol, 1.0 eq) was dissolved in EtOH (10 mL) and water (8.0 mL). Sodium sulfite (2.21 g, 5.0 eq) was added. The mixture was heated to reflux for 16 hours, and concentrated. The residue was purified by reversed phase column (Diaion HP-20) using distilled water (200 ml) first, then 10% CH3CN in water and finally 20% CH3CN in water to give sodium (S)-2-(tert-butoxycarbonylamino)-4-(methylthio)butane-1-sulfonate (376 mg, 37%). 1H NMR (DMSO-d6, 300 MHz) d 6.75 (d, 1H, NH), 3.50 (br s, 1H, BocNHCH), 2.3-2.5 (m, 4H, SCH2 and OSCH2, overlapped with DMSO solvent peak), 2.0 (s, 3H, SCH3), 1.8 (m, 1H, NHCHCH2CH2S), 1.6 (m, 1H, NHCHCH2CH2S), 1.35 (s, 9H, OC(CH3)3). LC-MS: 2.03 min; MS (ESI−) m/z 298 (M-Na)+, 198 (M-Na-Boc)+.

Workup

  1. temperatureThe mixture was heated
  2. temperatureto reflux for 16 hours
  3. concentrationconcentrated
  4. customThe residue was purified by reversed phase column (Diaion HP-20)
  5. distillationusing distilled water (200 ml) first

Sources & evidence

ORD record
ord-d7450f449dfd4b95933c3eed2ff72f76
Source dataset
uspto-grants-2013_11
Patent number
US08580859B2

Reaction notes

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