Dimethylformamide → Tert-butyl 4-formylpyridin-3-ylcarbamate
Reaction equation
C([Li])(C)(C)C.[C:6]([O:10][C:11](=[O:19])[NH:12][C:13]1[CH:14]=[N:15][CH:16]=[CH:17][CH:18]=1)([CH3:9])([CH3:8])[CH3:7].CN(C)[CH:22]=[O:23]>C1COCC1>[C:6]([O:10][C:11](=[O:19])[NH:12][C:13]1[CH:14]=[N:15][CH:16]=[CH:17][C:18]=1[CH:22]=[O:23])([CH3:9])([CH3:7])[CH3:8]Participants
Reactant 3
Product 1
Reagents, catalysts & solvents 1
Conditions
- Temperature
- 0 °C
Procedure
tert-Butyllithium (1.7 M, 14.5 mL, 24.6 mmol, 2.39 equiv) was added to a solution of pyridin-3-yl-carbamic acid tert-butyl ester (6-1, 4.00 g, 20.6 mmol, 1 equiv) in THF (100 mL) at −78° C., and the resulting mixture stirred for 1 h. N,N-dimethylformamide (8.00 mL, 103 mmol, 5 equiv) was added, and the reaction mixture was warmed to 0° C. and stirred for 30 min. The mixture was partitioned between water (400 mL) and ethyl acetate (3×150 mL). The combined organic layers were dried over sodium sulfate and concentrated. The residue was purified by flash column chromatography (20% ethyl acetate in hexanes, grading to 40% ethyl acetate in hexanes) to afford (4-formyl-pyridin-3-yl)-carbamic acid tert-butyl ester (6-2) as a light yellow oil. 1H NMR (400 MHz, CDCl3) δ 10.00 (s, 1H), 9.89 (br s, 1H), 9.84 (s, 1H), 8.53 (d, 1H, J=4.8 Hz), 7.49 (d, 1H, J=4.8 Hz), 1.55 (s, 9H); TLC (EtOAc), Rf=0.47.
Workup
- stirringstirred for 30 min
- customThe mixture was partitioned between water (400 mL) and ethyl acetate (3×150 mL)
- dry with materialThe combined organic layers were dried over sodium sulfate
- concentrationconcentrated
- customThe residue was purified by flash column chromatography (20% ethyl acetate in hexanes, grading to 40% ethyl acetate in hexanes)
Sources & evidence
- ORD record
- ord-89ff2242a1664098a664cf5d316add2c
- Source dataset
- uspto-grants-2002_11
- Patent number
- US06479512B1
Reaction notes
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