Sodium Bicarbonate → 1,1-Dimethylethyl (1S)-1-[[(1,1-dimethylethoxy)carbonyl]amino]-4-oxo-2-cyclopentene-1-carboxylate

HRID 1690820Notes

Reaction equation

HRID 1690820 reaction equation
[C:1]([O:5][C:6]([NH:8][C@:9]1([C:15]([O:17][C:18]([CH3:21])([CH3:20])[CH3:19])=[O:16])[CH:13]=[CH:12][C@H:11]([OH:14])[CH2:10]1)=[O:7])([CH3:4])([CH3:3])[CH3:2].[O-]Cl.[Na+].C([O-])(O)=O.[Na+]>CC(OC)(C)C.[K+].[Br-]>[C:1]([O:5][C:6]([NH:8][C@:9]1([C:15]([O:17][C:18]([CH3:21])([CH3:20])[CH3:19])=[O:16])[CH:13]=[CH:12][C:11](=[O:14])[CH2:10]1)=[O:7])([CH3:4])([CH3:3])[CH3:2]

Participants

6

Reactant 3

HCID 516892Sodium BicarbonateHCID 23665760Sodium HypochloriteHCID 66902327HCID 66902327, compound

Product 1

HCID 597129231,1-Dimethylethyl (1S)-1-[[(1,1-dimethylethoxy)carbonyl]amino]-4-oxo-2-cyclopentene-1-carboxylateYield 89%

Reagents, catalysts & solvents 2

HCID 253877Potassium BromideCatalystHCID 15413tert-Butyl methyl etherSolvent

Conditions

Temperature
0 °C

Procedure

Add 2,2,6,6-tetramethyl-1-piperidinyloxy (free radical) (TEMPO) (0.84 g, 5.3 mmol) and KBr (0.63 g, 5.3 mmol, in 2 mL of water) to a solution of (1S,3R)-1-(tert-butoxycarbonylamino)-1-(tert-butoxycarbonyl)-3-hydroxycyclopent-4-ene (20 g, 66.8 mmol) in MTBE (200 mL). Cool the reaction mixture to 0° C. and add a solution of NaOCl (3.14%, 240 g, 100 mmol) containing NaHCO3 (8.4 g) dropwise, keeping the temperature below 5° C. Stir the reaction 1 hour at 0° C. and allow to warm to room temperature. Separate the layers and extract the aqueous layer with MTBE (2×200 mL). Wash the combined organic layers with 200 mL of 1N HCl solution containing 2.21 g of KI followed by 10% Na2SO3 solution (200 mL). Wash the organic layer with water (2×200 mL) and concentrate to dryness under vacuum. Dissolve the crude product in MTBE (60 mL) at 50° C. and crystallize by addition of heptane (200 mL) over 1 h. Cool the mixture was cooled to 0° C. over 2 hours and then filter. Wash the filter cake with 100 mL of cold heptane:MTBE (65:35) and vacuum dry to give 16.99 g (89% yield) of the title compound as a white solid.

Workup

  1. customthe temperature below 5° C
  2. customthe reaction 1 hour at 0° C.
  3. temperatureto warm to room temperature
  4. customSeparate the layers
  5. extractionextract the aqueous layer with MTBE (2×200 mL)
  6. washWash the combined organic layers with 200 mL of 1N HCl solution
  7. additioncontaining 2.21 g of KI
  8. washWash the organic layer with water (2×200 mL)
  9. concentrationconcentrate to dryness under vacuum
  10. dissolutionDissolve the crude product in MTBE (60 mL) at 50° C.
  11. customcrystallize by addition of heptane (200 mL) over 1 h
  12. temperatureCool the mixture
  13. temperaturewas cooled to 0° C. over 2 hours
  14. filtrationfilter
  15. washWash the filter cake with 100 mL of cold heptane:MTBE (65:35) and vacuum
  16. customdry

Sources & evidence

ORD record
ord-f8dc24bf7b5a4ba3a2475799ef112c9a
Source dataset
uspto-grants-2012_04
Patent number
US08153683B2

Reaction notes

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