Sodium Thiosulfate → tert-Butyl [tert-butoxycarbonyl(6-formylpyridin-2-yl)amino]acetate

HRID 241291Notes

Reaction equation

HRID 241291 reaction equation
CC(OI1(OC(C)=O)(OC(C)=O)OC(=O)C2C=CC=CC1=2)=O.[C:23]([O:27][C:28](=[O:46])[CH2:29][N:30]([C:39]([O:41][C:42]([CH3:45])([CH3:44])[CH3:43])=[O:40])[C:31]1[CH:36]=[CH:35][CH:34]=[C:33]([CH2:37][OH:38])[N:32]=1)([CH3:26])([CH3:25])[CH3:24].S([O-])([O-])(=O)=S.[Na+].[Na+]>C(Cl)Cl>[C:23]([O:27][C:28](=[O:46])[CH2:29][N:30]([C:39]([O:41][C:42]([CH3:45])([CH3:44])[CH3:43])=[O:40])[C:31]1[CH:36]=[CH:35][CH:34]=[C:33]([CH:37]=[O:38])[N:32]=1)([CH3:26])([CH3:25])[CH3:24]

Participants

5

Reactant 3

HCID 24477Sodium ThiosulfateHCID 159087TriacetoxyperiodinaneHCID 86651768Tert-butyl[tert-butoxycarbonyl(6-hydroxymethylpyridin-2-yl)amino]acetate

Product 1

HCID 86651795tert-Butyl [tert-butoxycarbonyl(6-formylpyridin-2-yl)amino]acetateYield 96.5%

Reagents, catalysts & solvents 1

HCID 6344DichloromethaneSolvent2×

Procedure

To a solution of Dess-martin reagent (12.9 g, 30.4 mmol) in methylene chloride (130 ml) was added dropwise a solution of tert-butyl[tert-butoxycarbonyl(6-hydroxymethylpyridin-2-yl)amino]acetate (10.0 g, 29.6 mmol) obtained in Reference Example 3-(b) in methylene chloride (50 ml) over 20 minutes under ice cooling in argon atmosphere. After completion of the dropwise addition, the mixture was stirred at room temperature for 2 hours. After completion of the reaction, a 0.1% aqueous sodium thiosulfate solution (305 ml) was added to the reaction solution, followed by extraction with methylene chloride. The separated organic layer was washed sequentially with a 0.5N aqueous sodium hydroxide solution and a saturated aqueous sodium chloride solution, dried over anhydrous magnesium sulfate, and then concentrated under reduced pressure to afford the title compound (9.61 g) substantially quantitatively as a slightly yellow oil.

Workup

  1. additionAfter completion of the dropwise addition
  2. customAfter completion of the reaction
  3. extractionfollowed by extraction with methylene chloride
  4. washThe separated organic layer was washed sequentially with a 0.5N aqueous sodium hydroxide solution
  5. dry with materiala saturated aqueous sodium chloride solution, dried over anhydrous magnesium sulfate
  6. concentrationconcentrated under reduced pressure

Sources & evidence

ORD record
ord-9fa938f68eb849caa5020513ed999cb1
Source dataset
uspto-grants-2014_02
Patent number
US08648097B2

Reaction notes

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