Hydrochloric Acid → Tert-butyl(2s,3s)-3(tert-butyldimethylsilyloxy)-4-hydroxy-1-((s)-tetrahydrofuran-3-yl)butan-2-ylcarbamate

HRID 1039731Notes

Reaction equation

HRID 1039731 reaction equation
[Si:1]([O:8][C@H:9]([CH2:24][O:25][Si](C(C)(C)C)(C)C)[C@@H:10]([NH:17][S@](C(C)(C)C)=O)[CH2:11][CH:12]1[CH2:16][CH2:15][O:14][CH2:13]1)([C:4]([CH3:7])([CH3:6])[CH3:5])([CH3:3])[CH3:2].Cl.[C:34]([O:38][C:39](O[C:42]([O:44][C:45]([CH3:48])([CH3:47])[CH3:46])=[O:43])=[O:40])([CH3:37])([CH3:36])[CH3:35]>CO.C(Cl)Cl>[Si:1]([O:8][C@H:9]([CH2:24][OH:25])[C@@H:10]([NH:17][C:39](=[O:40])[O:38][C:34]([CH3:37])([CH3:36])[CH3:35])[CH2:11][C@H:12]1[CH2:16][CH2:15][O:14][CH2:13]1)([C:4]([CH3:5])([CH3:6])[CH3:7])([CH3:2])[CH3:3].[Si:1]([O:8][C@H:9]([CH2:24][OH:25])[C@@H:10]([NH:17][C:42](=[O:43])[O:44][C:45]([CH3:46])([CH3:47])[CH3:48])[CH2:11][C@@H:12]1[CH2:16][CH2:15][O:14][CH2:13]1)([C:4]([CH3:6])([CH3:7])[CH3:5])([CH3:3])[CH3:2]

Participants

7

Reactant 3

HCID 313Hydrochloric AcidHCID 90495Di-tert-butyl dicarbonateHCID 67270703(S)-N-((2S,3S)-3,4-bis(tert-butyldimethylsilyloxy)-1-(tetrahydrofuran-3-yl)butan-2-yl)-2-methylpropane-2-sulfinamide

Product 2

HCID 131729657Tert-butyl(2s,3s)-3(tert-butyldimethylsilyloxy)-4-hydroxy-1-((s)-tetrahydrofuran-3-yl)butan-2-ylcarbamateHCID 131729658Tert-butyl(2s,3s)-3 (tert-butyldimethylsilyloxy)-4-hydroxy-1-((r)-tetrahydrofuran-3-yl)butan-2-ylcarbamate

Reagents, catalysts & solvents 2

HCID 887MethanolSolventHCID 6344DichloromethaneSolvent

Procedure

A solution of (S)-N-((2S,3S)-3,4-bis(tert-butyldimethylsilyloxy)-1-(tetrahydrofuran-3-yl)butan-2-yl)-2-methylpropane-2-sulfinamide (1.5 g, 3.0 mmol) in dry MeOH (30 mL) was brought to −20° C. followed by the addition of 10% HCl (100 mL, MeOH/acetyl chloride) and the resulting mixture was stirred at −20 C for 1 h. The mixture was quenched with 10% Na2CO3 and extracted with DCM (8×). The combined organics were dried over Na2CO4, filtered, concentrated and colorless oil obtained was dissolved in DCM (30 mL) followed by the addition of TEA (1.2 mL, 8.9 mmol) and di-tert-butyldicarbonate (1.0 mL, 4.4 mmol). The reaction was stirred at RT for 17 h. The mixture was concentrated and chromatographed on silica gel using 4:1 to 1:1 EtOAc/hexanes to afford a colorless oil as tert-butyl(2S,3S)-3(tert-butyldimethylsilyloxy)-4-hydroxy-1-((S)-tetrahydrofuran-3-yl)butan-2-ylcarbamate AND Tert-butyl(2S,3S)-3 (tert-butyldimethylsilyloxy)-4-hydroxy-1-((R)-tetrahydrofuran-3-yl)butan-2-ylcarbamate.

Workup

  1. customwas brought to −20° C.
  2. customThe mixture was quenched with 10% Na2CO3
  3. extractionextracted with DCM (8×)
  4. dry with materialThe combined organics were dried over Na2CO4
  5. filtrationfiltered
  6. concentrationconcentrated
  7. customcolorless oil obtained
  8. stirringThe reaction was stirred at RT for 17 h
  9. concentrationThe mixture was concentrated
  10. customchromatographed on silica gel using 4:1 to 1:1 EtOAc/hexanes

Sources & evidence

ORD record
ord-4fcdbcc21b874a2780b4a2aab11ddf6e
Source dataset
uspto-grants-2013_10
Patent number
US08552181B2

Reaction notes

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