Hydrogen Peroxide → Di-tert-butyl (2S,4S)-2-(Boc-amino)-4-(3-hydroxypropyl)pentanedioate

HRID 625829Notes

Reaction equation

HRID 625829 reaction equation
[CH2:1]([C@H:4]([C:22]([O:24][C:25]([CH3:28])([CH3:27])[CH3:26])=[O:23])[CH2:5][C@H:6]([NH:14][C:15]([O:17][C:18]([CH3:21])([CH3:20])[CH3:19])=[O:16])[C:7]([O:9][C:10]([CH3:13])([CH3:12])[CH3:11])=[O:8])[CH:2]=[CH2:3].[OH-:29].[Na+].OO>O1CCCC1.O>[C:18]([O:17][C:15]([NH:14][C@@H:6]([CH2:5][C@H:4]([CH2:1][CH2:2][CH2:3][OH:29])[C:22]([O:24][C:25]([CH3:28])([CH3:27])[CH3:26])=[O:23])[C:7]([O:9][C:10]([CH3:13])([CH3:12])[CH3:11])=[O:8])=[O:16])([CH3:21])([CH3:20])[CH3:19]

Participants

6

Reactant 3

HCID 784Hydrogen PeroxideHCID 14798Sodium HydroxideHCID 58185190Di-tert-butyl (2S,4S)-2-Allyl-4-(Boc-amino)pentanedioate

Product 1

HCID 58185183Di-tert-butyl (2S,4S)-2-(Boc-amino)-4-(3-hydroxypropyl)pentanedioate

Reagents, catalysts & solvents 2

HCID 962WaterSolventHCID 8028TetrahydrofuranSolvent2×

Procedure

15.58 g (39 mmol) of di-tert-butyl (2S,4S)-4-allyl-2-tert-butoxycarbonylamino-pentanedioate 5a were dissolved in 200 mL of tetrahydrofuran (THF) and cooled in an ice-bath. Over a period of about 20 minutes, 54.6 mL (54.6 mmol) of 1 M diboran/tetrahydrofuran complex in tetrahydrofuran were added dropwise with ice-cooling and under nitrogen, and the mixture was stirred on ice for 2 h and at room temperature overnight. It was cooled again to 0° C. and 58.5 mL of 1 N aqueous sodium hydroxide solution and 58.5 mL of 30% aqueous hydrogen peroxide solution were then added dropwise. After 60 minutes, the mixture was diluted with water, the tetrahydrofuran was distilled off and the remaining aqueous solution was extracted with ethyl acetate. The organic phase was separated off, washed with water until neutral, dried over sodium sulphate and filtered, and the filtrate was concentrated. The crude product obtained in this manner was chromatographed on silica gel using a hexane/ethyl acetate gradient, and the appropriate fractions were combined and concentrated.

Workup

  1. temperaturecooled in an ice-bath
  2. temperaturecooling and under nitrogen
  3. temperatureIt was cooled again to 0° C.
  4. waitAfter 60 minutes
  5. distillationthe tetrahydrofuran was distilled off
  6. extractionthe remaining aqueous solution was extracted with ethyl acetate
  7. customThe organic phase was separated off
  8. washwashed with water until neutral,
  9. dry with materialdried over sodium sulphate
  10. filtrationfiltered
  11. concentrationthe filtrate was concentrated

Sources & evidence

ORD record
ord-3e9d647c648543a5914d9337fa593020
Source dataset
uspto-grants-2016_04
Patent number
US09308282B2

Reaction notes

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