Sodium Bicarbonate → HCID 117607812, compound

HRID 58851Notes

Reaction equation

HRID 58851 reaction equation
[F:1][C:2]1([F:21])[CH2:5][CH:4]([CH2:6][C@H:7]([NH:13][C:14](=[O:20])[O:15][C:16]([CH3:19])([CH3:18])[CH3:17])[C:8](=[O:12])[C:9]([CH3:11])=[CH2:10])[CH2:3]1.[O-]Cl.[Na+].C(=O)(O)[O-:26].[Na+]>CN(C=O)C>[F:1][C:2]1([F:21])[CH2:3][CH:4]([CH2:6][C@H:7]([NH:13][C:14](=[O:20])[O:15][C:16]([CH3:17])([CH3:19])[CH3:18])[C:8]([C@@:9]2([CH3:11])[CH2:10][O:26]2)=[O:12])[CH2:5]1

Participants

5

Reactant 3

HCID 516892Sodium BicarbonateHCID 23665760Sodium HypochloriteHCID 117607811HCID 117607811, compound

Product 1

HCID 117607812HCID 117607812, compoundYield 62%

Reagents, catalysts & solvents 1

HCID 6228DimethylformamideSolvent

Conditions

Temperature
0 °C

Procedure

A solution of (S)-tert-butyl 1-(3,3-difluorocyclobutyl)-4-methyl-3-oxopent-4-en-2-ylcarbamate (0.80 g, 2.6 mmol) in DMF (20 mL) was cooled to 0° C. and 10% aqueous NaClO solution (7.90 mL, 10.6 mmol) was added while keeping the internal temperature below 5° C. The reaction mixture was stirred for 1 h at 0° C. and poured into saturated aqueous sodium bicarbonate (50 mL). The resulting mixture was extracted with EtOAc (50 mL×3). The organic extracts were combined, washed with brine (100 mL×2), dried over anhydrous sodium sulfate, and concentrated. The residue was purified by flash column chromatography on silica gel (petroleum ether/EtOAc=200:1 to 50:1) to afford tert-butyl ((S)-3-(3,3-difluorocyclobutyl)-1-((R)-2-methyloxiran-2-yl)-1-oxopropan-2-yl)carbamate (510 mg, 62% yield). 1H NMR (300 MHz, CDCl3): δ 5.02 (d, J=8.7 Hz, 1H), 4.25 (m, 1H), 3.23 (d, J=4.5 Hz, 1H), 2.93 (d, J=4.8 Hz, 1H), 2.73 (m, 2H), 2.25 (m, 3H), 1.92 (m, 1H), 1.55 (m, 1H), 1.54 (s, 3H), 1.43 (s, 9H). MS (EI) for C15H23F2NO4, found 358.14 [M+K]+.

Workup

  1. customthe internal temperature below 5° C
  2. extractionThe resulting mixture was extracted with EtOAc (50 mL×3)
  3. washwashed with brine (100 mL×2)
  4. dry with materialdried over anhydrous sodium sulfate
  5. concentrationconcentrated
  6. customThe residue was purified by flash column chromatography on silica gel (petroleum ether/EtOAc=200:1 to 50:1)

Sources & evidence

ORD record
ord-e9119b8d10ac45dc94a501d423c65b81
Source dataset
uspto-grants-2016_09
Patent number
US09434761B2

Reaction notes

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