Ammonium Acetate → [(S)-1-(2-{(4-borono-phenyl)-[(E)-(3-phenylacryloyl)]amino}acetyl)pyrrolidin-3-yl]carbamic acid, tert-butyl ester

HRID 655180Notes

Reaction equation

HRID 655180 reaction equation
I([O-])(=O)(=O)=O.[Na+].C([O-])(=O)C.[NH4+].CC1(C)C(C)(C)[O:16][B:15]([C:20]2[CH:25]=[CH:24][C:23]([N:26]([C:43](=[O:52])/[CH:44]=[CH:45]/[C:46]3[CH:51]=[CH:50][CH:49]=[CH:48][CH:47]=3)[CH2:27][C:28]([N:30]3[CH2:34][CH2:33][C@H:32]([NH:35][C:36](=[O:42])[O:37][C:38]([CH3:41])([CH3:40])[CH3:39])[CH2:31]3)=[O:29])=[CH:22][CH:21]=2)[O:14]1>O.CC(C)=O>[B:15]([C:20]1[CH:21]=[CH:22][C:23]([N:26]([C:43](=[O:52])/[CH:44]=[CH:45]/[C:46]2[CH:51]=[CH:50][CH:49]=[CH:48][CH:47]=2)[CH2:27][C:28]([N:30]2[CH2:34][CH2:33][C@H:32]([NH:35][C:36](=[O:42])[O:37][C:38]([CH3:41])([CH3:40])[CH3:39])[CH2:31]2)=[O:29])=[CH:24][CH:25]=1)([OH:14])[OH:16]

Participants

6

Reactant 3

HCID 517165Ammonium AcetateHCID 23667635Sodium periodateHCID 59212034[(S)-1-(2-{[4-(4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl)phenyl]-[(E)-(3-phenylacryloyl)]amino}acetyl)pyrrolidin-3-yl]-carbamic acid, tert-butyl ester

Product 1

HCID 59211964[(S)-1-(2-{(4-borono-phenyl)-[(E)-(3-phenylacryloyl)]amino}acetyl)pyrrolidin-3-yl]carbamic acid, tert-butyl esterYield 80%

Reagents, catalysts & solvents 2

HCID 180AcetoneSolventHCID 962WaterSolvent

Procedure

Sodium periodate (2.06 g, 9.6 mmol) and ammonium acetate (0.74 g, 9.6 mmol) in water (20 mL) were added to [(S)-1-(2-{[4-(4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl)phenyl]-[(E)-(3-phenylacryloyl)]amino}acetyl)pyrrolidin-3-yl]-carbamic acid, tert-butyl ester 4 (1.85 g, 3.2 mmol) in acetone (30 mL) and the reaction stirred at room temperature for 64 h. The reaction mixture was concentrated in vacuo and 1M NaOH was added. The mixture was stirred for 4 h and then shaken with dichloromethane and filtered. The two layers were separated and the NaOH layer washed with dichloromethane. The aqueous basic layer was acidified to pH1 with conc. hydrochloric acid and extracted with ethyl acetate (×2). The combined organic layers were washed with brine, dried (Na2SO4) and evaporated to dryness. The resultant residue was purified by flash column chromatography on silica gel, eluting with ethyl acetate→5% methanol/ethyl acetate→10% methanol/ethyl acetate→methanol, to give the title compound as a glass (1.26 g, 80%) which was used directly in the next stage.

Workup

  1. concentrationThe reaction mixture was concentrated in vacuo and 1M NaOH
  2. additionwas added
  3. stirringThe mixture was stirred for 4 h
  4. stirringshaken with dichloromethane
  5. filtrationfiltered
  6. customThe two layers were separated
  7. washthe NaOH layer washed with dichloromethane
  8. extractionextracted with ethyl acetate (×2)
  9. washThe combined organic layers were washed with brine
  10. dry with materialdried (Na2SO4)
  11. customevaporated to dryness
  12. customThe resultant residue was purified by flash column chromatography on silica gel
  13. washeluting with ethyl acetate→5% methanol/ethyl acetate→10% methanol/ethyl acetate→methanol

Sources & evidence

ORD record
ord-93a68e5139a14e50a0ade62a2a0e642a
Source dataset
uspto-grants-2011_12
Patent number
US08071582B2

Reaction notes

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