Acetic Acid → HCID 57667101, compound

HRID 600852Notes

Reaction equation

HRID 600852 reaction equation
[C:1]([O:5][C:6]([N:8]1[C@@H:12]([CH2:13][NH:14][C:15]2[CH:20]=[CH:19][CH:18]=[C:17]([Cl:21])[N:16]=2)[CH2:11][O:10][C:9]1([CH3:23])[CH3:22])=[O:7])([CH3:4])([CH3:3])[CH3:2].[CH:24](=O)[CH3:25].C(O[BH-](OC(=O)C)OC(=O)C)(=O)C.[Na+].C(O)(=O)C>ClCCCl.C(Cl)Cl>[C:1]([O:5][C:6]([N:8]1[C@@H:12]([CH2:13][N:14]([C:15]2[CH:20]=[CH:19][CH:18]=[C:17]([Cl:21])[N:16]=2)[CH2:24][CH3:25])[CH2:11][O:10][C:9]1([CH3:23])[CH3:22])=[O:7])([CH3:4])([CH3:2])[CH3:3]

Participants

7

Reactant 4

HCID 176Acetic AcidHCID 177AcetaldehydeHCID 5049666Sodium triacetoxyborohydrideHCID 57667087HCID 57667087, compound

Product 1

HCID 57667101HCID 57667101, compoundYield 43%

Reagents, catalysts & solvents 2

HCID 111,2-DichloroethaneSolventHCID 6344DichloromethaneSolvent

Procedure

To a stirred solution of (S)-4-[(6-chloro-pyridin-2-ylamino)-methyl]-2,2-dimethyl-oxazo-lidine-3-carboxylic acid tert-butyl ester (528 mg) at r.t. in 1,2-dichloroethane (20 ml) under an argon atmosphere were added molecular sieves 4 A (˜2 g) and acetaldehyde (044 ml). After 30 min stirring at r.t., sodium triacetoxyborohydride (1.02 g) was added, followed by acetic acid (0.13 ml). The mixture was stirred for at r.t. over night, then diluted with CH2Cl2 and washed with sat. aq. Na2CO3. The biphasic mixture was filtered. The aqueous phase of the filtrate was back extracted with CH2Cl2. The combined organics were washed with brine, dried over MgSO4, filtered and concentrated. The crude product was purified by column chromatography (SiO2; gradient:cyclohexane->cyclohexane/EtOAc 85:15) to give (S)-4-{[(6-chloro-pyridin-2-yl)-ethyl-amino]-methyl}-2,2-dimethyl-oxazolidine-3-carboxylic acid tert-butyl ester (244 mg, 43%) as viscous yellow oil. MS (ISP): 370.3 ([M+H]+)

Workup

  1. stirringThe mixture was stirred for at r.t. over night
  2. washwashed with sat. aq. Na2CO3
  3. filtrationThe biphasic mixture was filtered
  4. extractionThe aqueous phase of the filtrate was back extracted with CH2Cl2
  5. washThe combined organics were washed with brine
  6. dry with materialdried over MgSO4
  7. filtrationfiltered
  8. concentrationconcentrated
  9. customThe crude product was purified by column chromatography (SiO2; gradient:cyclohexane->cyclohexane/EtOAc 85:15)

Sources & evidence

ORD record
ord-0b66e35b872149e48bc0d6c0a099a863
Source dataset
uspto-grants-2011_03
Patent number
US07902238B2

Reaction notes

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