Formaldehyde → HCID 57667117, compound

HRID 600843Notes

Reaction equation

HRID 600843 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]=[CH:17][CH:16]=2)[CH2:11][O:10][C:9]1([CH3:22])[CH3:21])=[O:7])([CH3:4])([CH3:3])[CH3:2].C=O.[BH3-][C:26]#N.[Na+]>CO.[Cl-].[Zn+2].[Cl-]>[C:1]([O:5][C:6]([N:8]1[C@@H:12]([CH2:13][N:14]([CH3:26])[C:15]2[CH:16]=[CH:17][CH:18]=[CH:19][CH:20]=2)[CH2:11][O:10][C:9]1([CH3:22])[CH3:21])=[O:7])([CH3:4])([CH3:2])[CH3:3]

Participants

6

Reactant 3

HCID 712FormaldehydeHCID 5003444Sodium cyanoborohydrideHCID 57667036HCID 57667036, compound

Product 1

HCID 57667117HCID 57667117, compoundYield 88.4%

Reagents, catalysts & solvents 2

HCID 3007855ZincchlorideCatalystHCID 887MethanolSolvent

Conditions

Temperature
40 °C

Procedure

To a stirred solution of (S)-2,2-dimethyl-4-phenylaminomethyl-oxazolidine-3-carboxylic acid tert-butyl ester (500 mg; example 2.a) at r.t. in methanol (10 ml) under an argon atmosphere were added formaldehyde (37% solution in H2O; 0.62 ml), zinc chloride (890 mg) and NaBH3CN (308 mg). The mixture was heated to 40° C. and stirring at that temperature was continued for 2 h. The mixture was concentrated and the residue was taken up in EtOAc/H2O. The biphasic mixture was filtered. The aqueous layer from the filtrate was back extracted with EtOAc. The combined organics were washed with brine, dried over MgSO4, filtered and concentrated. The crude product was purified by column chromatography (silica gel; gradient:cyclohexane->cyclohexane/EtOAc 85:15) to give (S)-2,2-dimethyl-4-[(methyl-phenyl-amino)-methyl]-oxazolidine-3-carboxylic acid tert-butyl ester (462 mg, 88%) as colorless viscous oil. MS (ISP): 321.4 ([M+H]+)

Workup

  1. concentrationThe mixture was concentrated
  2. filtrationThe biphasic mixture was filtered
  3. extractionThe aqueous layer from the filtrate was back extracted with EtOAc
  4. washThe combined organics were washed with brine
  5. dry with materialdried over MgSO4
  6. filtrationfiltered
  7. concentrationconcentrated
  8. customThe crude product was purified by column chromatography (silica gel; gradient:cyclohexane->cyclohexane/EtOAc 85:15)

Sources & evidence

ORD record
ord-ee4b369a8e9b46938f4ecb3d14979687
Source dataset
uspto-grants-2011_03
Patent number
US07902238B2

Reaction notes

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