Sulfuric Acid → HCID 10807344, compound

HRID 1492826Notes

Reaction equation

HRID 1492826 reaction equation
[H-].[Na+].[C:3]([O:7][C:8]([N:10]1[CH2:14][C@H:13]([O:15][Si:16]([C:19]([CH3:22])([CH3:21])[CH3:20])([CH3:18])[CH3:17])[CH2:12][C@@H:11]1[CH2:23][CH2:24][N+]([O-])=O)=[O:9])([CH3:6])([CH3:5])[CH3:4].[Mn]([O-])(=O)(=O)=[O:29].[K+].B(O)(O)O.O.O.O.O.O.S([O-])([O-])(=O)=S.[Na+].[Na+].S(=O)(=O)(O)O>C(O)(C)(C)C.O.CCCCCCC>[C:3]([O:7][C:8]([N:10]1[CH2:14][C@H:13]([O:15][Si:16]([C:19]([CH3:22])([CH3:21])[CH3:20])([CH3:18])[CH3:17])[CH2:12][C@H:11]1[CH2:23][CH:24]=[O:29])=[O:9])([CH3:6])([CH3:5])[CH3:4]

Participants

10

Reactant 6

HCID 1118Sulfuric AcidHCID 7628Boric AcidHCID 24758Sodium hydrideHCID 61475Sodium Thiosulfate PentahydrateHCID 516875Potassium PermanganateHCID 18657885HCID 18657885, compound

Product 1

HCID 10807344HCID 10807344, compoundYield 66%

Reagents, catalysts & solvents 3

HCID 962WaterSolvent3×HCID 6386tert-ButanolSolvent2×HCID 8900HeptaneSolvent

Procedure

To 60% sodium hydride (2.56 g, 64 mmol), tert-butylalcohol (50 ml) was added in a nitrogen stream at room temperature and the mixture was stirred for 20 minutes. To this mixture, a solution of (2S,4R)-N-tert-butoxycarbonyl-4-tert-butyldimethylsiloxy-2-(2-nitroethyl)pyrrolidine (11.8 g, 32 mmol) in tert-butylalcohol (30 ml) was added at room temperature. After stirring for 20 minutes, the mixture was added to precooled heptane (1 l) in an ice-bath and further stirred for to minutes at 0° C.. To the reaction mixture, a solution of potassium permanganate (5.06 g, 32 mmol) in water (100 ml) and a solution of boric acid (3.94 g, 64 mmol) in water (50 ml) were added, and the mixture stirred for minutes. To the reaction mixture, a solution of sodium thiosulfate pentahydrate (15.88 g, 64 mmol) in water ml) and 1 N sulfuric acid (64 ml) were added. After stirring for 10 minutes, the reaction mixture was filtered with celite and washed with heptane (200 ml). The filtrate and washings were combined, and the organic layer was washed sequentially with a saturated sodium hydrogencarbonate aqueous solution (200 ml) and a saturated sodium chloride aqueous solution (200 ml), dried over anhydrous sodium sulfate and concentrated under reduced pressure. The obtained oily residue was subjected to silica gel column chromatography (Wakogel™ C-300, heptane-ethyl acetate 5:1) to obtain (2S,4R)-N-tert-butoxycarbonyl-4-tert-butyldimethylsiloxy-2-(formylmethyl)pyrrolidine (7.0 g, yield: 66%).

Workup

  1. stirringAfter stirring for 20 minutes
  2. stirringfurther stirred for to minutes at 0° C.
  3. stirringthe mixture stirred for minutes
  4. stirringAfter stirring for 10 minutes
  5. filtrationthe reaction mixture was filtered with celite
  6. washwashed with heptane (200 ml)
  7. washthe organic layer was washed sequentially with a saturated sodium hydrogencarbonate aqueous solution (200 ml)
  8. dry with materiala saturated sodium chloride aqueous solution (200 ml), dried over anhydrous sodium sulfate
  9. concentrationconcentrated under reduced pressure

Sources & evidence

ORD record
ord-292b1feb38f84682869016f3c12bcb5f
Source dataset
uspto-grants-1994_12
Patent number
US05374720

Reaction notes

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