Dimethylformamide → tert-Butyl (6-formylpyridin-2-yl)carbamate

HRID 1258605Notes

Reaction equation

HRID 1258605 reaction equation
Br[C:2]1[N:7]=[C:6]([NH:8][C:9](=[O:15])[O:10][C:11]([CH3:14])([CH3:13])[CH3:12])[CH:5]=[CH:4][CH:3]=1.[Li]C.[Li]CCCC.CN([CH:26]=[O:27])C>C1COCC1>[CH:26]([C:2]1[N:7]=[C:6]([NH:8][C:9](=[O:15])[O:10][C:11]([CH3:14])([CH3:13])[CH3:12])[CH:5]=[CH:4][CH:3]=1)=[O:27]

Participants

6

Reactant 4

HCID 6228DimethylformamideHCID 13040380Tert-butyl (6-bromopyridin-2-YL)carbamateHCID 178418339ButyllithiumHCID 178418348HCID 178418348, compound

Product 1

HCID 17832129tert-Butyl (6-formylpyridin-2-yl)carbamateYield 103.7%

Reagents, catalysts & solvents 1

HCID 8028TetrahydrofuranSolvent

Procedure

To a solution of tert-butyl (6-bromopyridin-2-yl)carbamate (15.960 g, 58.43 mmol, 1 eq.) in 300 ml of THF cooled to −78° C. was added MeLi (1.6 M, 36.52 ml, 58.43 mmol, 1 eq.) dropwise and stirring allowed for 30 min. Then BuLi (1.6 M, 40.17 ml, 64.27 mmol, 1.1 eq.) was added dropwise and stirring allowed for 1 h. DMF (9.36 g, 128.55 mmol, 2.2 eq.) was added and the mixture was stirred 30 min at −78° C. and 1 h at r.t. The reaction was quenched with sat. aqueous NH4Cl, and DCM was added. The aqueous layer was extracted with DCM and then organics were combined, dried over MgSO4 and concentrated to give tert-butyl (6-formylpyridin-2-yl)carbamate (13.46 g) as a clear oil that was used directly in next step.

Workup

  1. stirringstirring
  2. waitallowed for 1 h
  3. stirringthe mixture was stirred 30 min at −78° C. and 1 h at r.t
  4. customThe reaction was quenched with sat. aqueous NH4Cl, and DCM
  5. additionwas added
  6. extractionThe aqueous layer was extracted with DCM
  7. dry with materialdried over MgSO4
  8. concentrationconcentrated

Sources & evidence

ORD record
ord-0289584eba214ff6a0d2ca570b97c8d6
Source dataset
uspto-grants-2013_06
Patent number
US08466176B2

Reaction notes

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