Benzyloxyamine hydrochloride → (s)-2-[(3s,4r)-3-Benzyloxyiminomethyl-4-butyl-2-oxopyrrolidin-1-yl]-3,3,n,n-tetramethyl butyramide

HRID 273197Notes

Reaction equation

HRID 273197 reaction equation
C(O[CH2:9][C@@H:10]1[C@@H:14]([CH2:15][CH2:16][CH2:17][CH3:18])[CH2:13][N:12]([C@@H:19]([C:25]([CH3:28])([CH3:27])[CH3:26])[C:20]([N:22]([CH3:24])[CH3:23])=[O:21])[C:11]1=[O:29])C1C=CC=CC=1.CC(OI1(OC(C)=O)(OC(C)=O)OC(=O)C2C=CC=CC1=2)=O.Cl.[CH2:53]([O:60][NH2:61])[C:54]1[CH:59]=[CH:58][CH:57]=[CH:56][CH:55]=1>CO.[Pd].ClCCl.[OH-].[Na+].ClCCl>[CH2:53]([O:60][N:61]=[CH:9][C@@H:10]1[C@@H:14]([CH2:15][CH2:16][CH2:17][CH3:18])[CH2:13][N:12]([C@@H:19]([C:25]([CH3:27])([CH3:26])[CH3:28])[C:20]([N:22]([CH3:23])[CH3:24])=[O:21])[C:11]1=[O:29])[C:54]1[CH:59]=[CH:58][CH:57]=[CH:56][CH:55]=1

Participants

8

Reactant 3

HCID 102312Benzyloxyamine hydrochlorideHCID 159087TriacetoxyperiodinaneHCID 69316026(S)-2-[(3S,4R)-3-Benzyloxymethyl-4-butyl-2-oxopyrrolidin-1-yl]-3,3, N,N-tetramethyl butyramide

Product 1

HCID 87780216(s)-2-[(3s,4r)-3-Benzyloxyiminomethyl-4-butyl-2-oxopyrrolidin-1-yl]-3,3,n,n-tetramethyl butyramideYield 61%

Reagents, catalysts & solvents 4

HCID 23938PalladiumCatalystHCID 887MethanolSolventHCID 6344DichloromethaneSolventHCID 23721229Sodium hydroxide methylene chlorideSolvent

Procedure

(S)-2-[(3S,4R)-3-Benzyloxymethyl-4-butyl-2-oxopyrrolidin-1-yl]-3,3, N,N-tetramethyl butyramide (0.08 g, 0.2 mmol) was dissolved in methanol (2 mL) and stirred overnight under a hydrogen balloon in the presense of palladium on activated carbon (15 mg). Filtration followed by concentration provided a crude alcohol (58 mg) which was dissolved in dichloromethane (5 mL) and treated with Dess-Martin periodinane (0.13 g, 0.3 mmol) at 0° C. After warning up to rt, the reaction was stirred overnight and the solvent was removed under vacuum. The residue was then dissolved in pyridine (5 mL) and benzyloxyamine hydrochloride (0.064 g, 0.4 mmol) was added. After 1 h, the reaction mixture was condensed to dryness, the residue was dissolved in 1 N aq. NaOH/dichloromethane (2:3, 15 mL). The organic phase was separated, the aqueous phase was extracted with dichloromethane (5 mL). The combined organic extracts were dried (Na2SO4), filtered and concentrated. Purification of the residue by HPLC afforded (S)-2-[(3S,4R)-3-benzyloxyiminomethyl-4-butyl-2-oxopyrrolidin-1-yl]-3,3,N,N-tetramethyl butyramide as a colorless oil (0.05 g, 61%). MS(ES) m/e 416 [M+H]+.

Workup

  1. filtrationFiltration
  2. concentrationfollowed by concentration
  3. customprovided a crude alcohol (58 mg) which
  4. customAfter warning up to rt
  5. customthe solvent was removed under vacuum
  6. dissolutionThe residue was then dissolved in pyridine (5 mL)
  7. waitAfter 1 h
  8. customcondensed to dryness
  9. customThe organic phase was separated
  10. extractionthe aqueous phase was extracted with dichloromethane (5 mL)
  11. dry with materialThe combined organic extracts were dried (Na2SO4)
  12. filtrationfiltered
  13. concentrationconcentrated
  14. customPurification of the residue by HPLC

Sources & evidence

ORD record
ord-103e1f6aae2b44ab96baa650e3c06205
Source dataset
uspto-grants-2008_11
Patent number
US07456211B2

Reaction notes

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