Water → tert-butyl (3aR,5S,6S,6aS)-6-bromo-3a-(hydroxymethyl)hexahydro-2H-cyclopenta[b]furan-5-ylcarbamate

HRID 1747145Notes

Reaction equation

HRID 1747145 reaction equation
[OH:1][CH2:2][CH2:3][C@@:4]1([CH2:17][OH:18])[CH2:8][C@H:7]([NH:9][C:10](=[O:16])[O:11][C:12]([CH3:15])([CH3:14])[CH3:13])[CH:6]=[CH:5]1.[Br:19]N1C(=O)CCC1=O.O>CCOC(C)=O>[Br:19][C@@H:6]1[C@H:5]2[O:1][CH2:2][CH2:3][C@@:4]2([CH2:17][OH:18])[CH2:8][C@@H:7]1[NH:9][C:10](=[O:16])[O:11][C:12]([CH3:15])([CH3:13])[CH3:14]

Participants

5

Reactant 3

HCID 962WaterHCID 67184N-bromobutanimideHCID 86708141tert-butyl ((1S,4S)-4-(2-hydroxyethyl)-4-(hydroxymethyl)cyclopent-2-en-1-yl)carbamate

Product 1

HCID 86708147tert-butyl (3aR,5S,6S,6aS)-6-bromo-3a-(hydroxymethyl)hexahydro-2H-cyclopenta[b]furan-5-ylcarbamate

Reagents, catalysts & solvents 1

HCID 8857Ethyl AcetateSolvent

Procedure

To a chilled solution of the product of Step F (343.60 g) in EtOAc (4 L) was added N-bromosuccinimide (237.60 g) followed by stirring at rt for 18 h. To the mixture was added water (5 mL) and the reaction heated to 60° C. for 30 min. The reaction was filtered, the filtrate was washed with aqueous sodium thiosulfate until the organic layer was negative for peroxides. The organic layer was washed with aqueous Na2CO3 (10%), dried (Na2SO4) and the reaction was concentrated under reduced pressure. Near the end of the concentration, heptane (1.2 L) was added, and the product was collected by filtration to provide the product of Step G. 1H NMR (400 MHz, CHLOROFORM-d) δ=4.78-4.91 (m, 1H), 4.41 (br. s., 1H), 4.31 (s, 2H), 3.88-3.98 (m, 1H), 3.61-3.77 (m, 3H), 2.08-2.24 (m, 1H), 1.82 (m, 2H), 1.60-1.70 (t, 1H), 1.45 (s, 9H)

Workup

  1. temperaturethe reaction heated to 60° C. for 30 min
  2. filtrationThe reaction was filtered
  3. washthe filtrate was washed with aqueous sodium thiosulfate until the organic layer
  4. washThe organic layer was washed with aqueous Na2CO3 (10%)
  5. dry with materialdried (Na2SO4)
  6. concentrationthe reaction was concentrated under reduced pressure
  7. concentrationNear the end of the concentration, heptane (1.2 L)
  8. additionwas added
  9. filtrationthe product was collected by filtration

Sources & evidence

ORD record
ord-5be5f0849f0141229085f3cc938711b9
Source dataset
uspto-grants-2015_10
Patent number
US09150532B2

Reaction notes

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