Methanol → N-Me-Tyr(3-tBu)-OMe

HRID 1988291Notes

Reaction equation

HRID 1988291 reaction equation
[NH:1]([CH:19]=O)[C@H:2]([C:15]([O:17][CH3:18])=[O:16])[CH2:3][C:4]1[CH:9]=[CH:8][C:7]([OH:10])=[C:6]([C:11]([CH3:14])([CH3:13])[CH3:12])[CH:5]=1.CO.Br.C(O)(=O)C.C([O-])(O)=O.[Na+]>C1COCC1>[NH:1]([CH3:19])[C@H:2]([C:15]([O:17][CH3:18])=[O:16])[CH2:3][C:4]1[CH:9]=[CH:8][C:7]([OH:10])=[C:6]([C:11]([CH3:14])([CH3:12])[CH3:13])[CH:5]=1

Participants

6

Reactant 4

HCID 887MethanolHCID 516892Sodium BicarbonateHCID 21893785Acetic Acid Mixture with Hydrobromic AcidHCID 131727520N-formyl-Tyr(3-tBu)-OMe

Product 1

HCID 131722749N-Me-Tyr(3-tBu)-OMeYield 90%

Reagents, catalysts & solvents 1

HCID 8028TetrahydrofuranSolvent

Procedure

To a solution of N-formyl-Tyr(3-tBu)-OMe (23.8 g, 85.3 mmol) in THF (400 ml), 1.0M borane-THF complex (170 ml) was added dropwise under cooling with ice over 30 min. The mixture was stirred for 20 min., mixed with methanol (50 ml) and further stirred for 30 min. The reaction mixture was mixed with 33% hydrobromic acid/acetic acid (31 ml) and stirred for 2 hours. The mixture was neutralized by saturated aqueous NaHCO3 under cooling with ice and extracted with chloroform. The organic layer was washed with saturated brine, dried over anhydrous magnesium sulfate and evaporated to remove the solvent under reduced pressure. The thus obtained residue was subjected to silica gel column chromatography (developing solvent: chloroform:methanol=20:1), giving N-Me-Tyr(3-tBu)-OMe (20.3 g, 90%).

Workup

  1. temperatureunder cooling with ice over 30 min
  2. stirringfurther stirred for 30 min
  3. stirringstirred for 2 hours
  4. temperatureunder cooling with ice
  5. extractionextracted with chloroform
  6. washThe organic layer was washed with saturated brine
  7. dry with materialdried over anhydrous magnesium sulfate
  8. customevaporated
  9. customto remove the solvent under reduced pressure

Sources & evidence

ORD record
ord-f75bb4f8ee014dbfb80b8a39ea189d7f
Source dataset
uspto-grants-2009_06
Patent number
US07553969B1

Reaction notes

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