Hydrogen Peroxide → 5-(Benzyloxy)-6-(4-methylthiazol-2-ylamino)pyridin-3-ol
Reaction equation
Cl.[CH2:2]([O:9][C:10]1[C:11]([NH:17][C:18]2[S:19][CH:20]=[C:21]([CH3:23])[N:22]=2)=[N:12][CH:13]=[C:14](Br)[CH:15]=1)[C:3]1[CH:8]=[CH:7][CH:6]=[CH:5][CH:4]=1.[Li]C.C([Li])CCC.C([O:34]B(OC(C)C)OC(C)C)(C)C.[OH-].[Na+].OO>CO.C1COCC1>[CH2:2]([O:9][C:10]1[CH:15]=[C:14]([OH:34])[CH:13]=[N:12][C:11]=1[NH:17][C:18]1[S:19][CH:20]=[C:21]([CH3:23])[N:22]=1)[C:3]1[CH:8]=[CH:7][CH:6]=[CH:5][CH:4]=1Participants
Reactant 6
Product 1
Reagents, catalysts & solvents 2
Conditions
- Temperature
- -78 °C
Procedure
3-(Benzyloxy)-5-bromo-N-(4-methylthiazol-2-yl)pyridin-2-amine (prepared according to Example 1; 1.00 g, 2.66 mmol) was added to THF (30 mL) and cooled to −78° C. MeLi (2.07 mL, 3.32 mmol) was slowly added, and the reaction mixture was stirred for 10 minutes. Butyllithium (1.33 mL, 3.32 mmol) was added, and the reaction mixture was stirred for 15 minutes. Triisopropylborate (0.613 mL, 2.66 mmol) was added, and the reaction mixture was stirred for 30 minutes. The reaction mixture was warmed to 0° C., and methanol (5 mL), 10% aqueous NaOH (5.1 mL, 12.8 mmol), and 30% aqueous H2O2 (1.27 mL, 13.3 mmol) were added. The reaction mixture was stirred at 0° C. for 1 hour, then purified by silica gel (10-20% EtOAc in hexanes) to give 5-(benzyloxy)-6-(4-methylthiazol-2-ylamino)pyridin-3-ol (0.198 g, 23.8% yield). 1H NMR (d6-DMSO) δ 7.59 (m, 3H), 7.40 (m, 3H), 7.17 (d, 1H), 6.84 (s, 1H), 5.31 (s, 2H), 2.33 (s, 3H). Mass spectrum (apci) m/z=314.1 (M+H).
Workup
- stirringthe reaction mixture was stirred for 15 minutes
- stirringthe reaction mixture was stirred for 30 minutes
- temperatureThe reaction mixture was warmed to 0° C.
- stirringThe reaction mixture was stirred at 0° C. for 1 hour
- custompurified by silica gel (10-20% EtOAc in hexanes)
Sources & evidence
- ORD record
- ord-ad8f967d1083480da6a9980b2d73b6a7
- Source dataset
- uspto-grants-2015_01
- Patent number
- US08933077B2
Reaction notes
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