Sodium Acetate → [(3R*,4S*,5S*)-5-(3-Fluoro-4-nitro-benzyl)-4-hydroxy-1,1-dioxo-hexahydro-1lambda*6*-thiopyran-3-yl]-carbamic acid tert-butyl ester

HRID 420267Notes

Reaction equation

HRID 420267 reaction equation
[C:1]([O:5][C:6](=[O:26])[NH:7][C@@H:8]1[C@H:13]([OH:14])[C@H:12]([CH2:15][C:16]2[CH:21]=[CH:20][C:19]([N+:22]([O-:24])=[O:23])=[C:18]([F:25])[CH:17]=2)[CH2:11]S[CH2:9]1)([CH3:4])([CH3:3])[CH3:2].O[O:28][S:29]([O-:31])=O.[K+].CC([O-])=O.[Na+].S(S([O-])=O)([O-])(=O)=O.[Na+].[Na+]>C1COCC1.O>[C:1]([O:5][C:6](=[O:26])[NH:7][C@@H:8]1[C@@H:13]([OH:14])[C@H:12]([CH2:15][C:16]2[CH:21]=[CH:20][C:19]([N+:22]([O-:24])=[O:23])=[C:18]([F:25])[CH:17]=2)[CH2:11][S:29](=[O:31])(=[O:28])[CH2:9]1)([CH3:3])([CH3:4])[CH3:2]

Participants

7

Reactant 4

HCID 517045Sodium AcetateHCID 656671Sodium PyrosulfiteHCID 23707502Potassium hydroxy sulfiteHCID 68553360[(3R*,4R*,5S*)-5-(3-Fluoro-4-nitro-benzyl)-4-hydroxy-tetrahydro-thiopyran-3-yl]-carbamic acid tert-butyl ester

Product 1

HCID 131729359[(3R*,4S*,5S*)-5-(3-Fluoro-4-nitro-benzyl)-4-hydroxy-1,1-dioxo-hexahydro-1lambda*6*-thiopyran-3-yl]-carbamic acid tert-butyl ester

Reagents, catalysts & solvents 2

HCID 962WaterSolventHCID 8028TetrahydrofuranSolvent

Conditions

Temperature
25 °C

Procedure

To a solution of [(3R*,4R*,5S*)-5-(3-fluoro-4-nitro-benzyl)-4-hydroxy-tetrahydro-thiopyran-3-yl]-carbamic acid tert-butyl ester (0.78 g, 2.0 mmol) in THF (15 mL) was added water (15 mL) and oxone (2.62 g, 4.2 mmol) and the reaction mixture was stirred for 2 h at 25° C. The excess oxone was destroyed after addition of 2 equivalents of NaOAc with sodium meta-bisulfite and the product was extracted with EtOAc. Combined extracts were washed with brine, dried over MgSO4 and evaporated. The title compound was obtained as a light yellow solid suitable for use in the next step: TLC (toluene-EtOAc 1:1) Rf=0.18; HPLC RtA=1.67 min; ESIMS [M+NH4]+=436; 1H NMR (600 MHz, DMSO-d6): δ 8.11 (t, 1H), 7.41 (d, 1H), 7.27 (d, 1H), 6.71 (d, 1H), 5.22 (d, 1H), 3.72 (m, 1H), 3.0-3.2 (m, 5H), 2.82 (s, 1H), 2.71 (dd, 1H), 2.17 (dd, 1H), 1.38 (s, 9H).

Workup

  1. customThe excess oxone was destroyed
  2. extractionthe product was extracted with EtOAc
  3. washCombined extracts were washed with brine
  4. dry with materialdried over MgSO4
  5. customevaporated

Sources & evidence

ORD record
ord-a2d887294b414eca82c8a64a64251e82
Source dataset
uspto-grants-2012_01
Patent number
US08093406B2

Reaction notes

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