Water → tert-butyl-3',3',6-trimethyl-5-nitro-3',6'-dihydro-3,4'-bipyridine-1'(2'H)-carboxylate

HRID 2387996Notes

Reaction equation

HRID 2387996 reaction equation
[C:1]([O:5][C:6]([N:8]1[CH2:13][CH:12]=[C:11](B2OC(C)(C)C(C)(C)O2)[C:10]([CH3:24])([CH3:23])[CH2:9]1)=[O:7])([CH3:4])([CH3:3])[CH3:2].Br[C:26]1[CH:27]=[C:28]([N+:33]([O-:35])=[O:34])[C:29]([CH3:32])=[N:30][CH:31]=1.P([O-])([O-])([O-])=O.[K+].[K+].[K+].O>O1CCOCC1.[Pd].C1(P(C2C=CC=CC=2)C2C=CC=CC=2)C=CC=CC=1.C1(P(C2C=CC=CC=2)C2C=CC=CC=2)C=CC=CC=1.C1(P(C2C=CC=CC=2)C2C=CC=CC=2)C=CC=CC=1.C1(P(C2C=CC=CC=2)C2C=CC=CC=2)C=CC=CC=1>[C:1]([O:5][C:6]([N:8]1[CH2:13][CH:12]=[C:11]([C:26]2[CH:31]=[N:30][C:29]([CH3:32])=[C:28]([N+:33]([O-:35])=[O:34])[CH:27]=2)[C:10]([CH3:23])([CH3:24])[CH2:9]1)=[O:7])([CH3:2])([CH3:3])[CH3:4]

Participants

7

Reactant 4

HCID 962WaterHCID 62657Potassium Phosphate, TribasicHCID 250672665-Bromo-2-methyl-3-nitropyridineHCID 59405002(1-(tert-Butoxycarbonyl)-3,3-dimethyl-1,2,3,6-tetrahydropyridin-4-yl)boronic acid pinacol ester

Product 1

HCID 59404975tert-butyl-3',3',6-trimethyl-5-nitro-3',6'-dihydro-3,4'-bipyridine-1'(2'H)-carboxylateYield 60%

Reagents, catalysts & solvents 2

HCID 11979704Tetrakis(triphenylphosphine)palladiumCatalystHCID 312751,4-DioxaneSolvent

Conditions

Temperature
80 °C

Procedure

To a solution of tert-butyl-3,3-dimethyl-4-(4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl)-3,6-dihydropyridine-1(2H)-carboxylate (2.12 g, 6.28 mmol) in 1,4-dioxane (90 mL) were added 5-bromo-2-methyl-3-nitropyridine (1.64 g, 7.54 mmol), tetrakis(triphenylphosphine) palladium (642 mg, 0.556 mmol), potassium phosphate (4.96 g, 23.4 mmol) and water (22 mL). The reaction mixture was flushed with nitrogen gas and allowed to stir for 24 h at 80° C. The reaction mixture was filtered through a Celite® pad and washed with DCM. The filtrate was washed with brine, dried over Na2SO4, filtered and concentrated. The residue was purified by column chromatography to give tert-butyl-3′,3′,6-trimethyl-5-nitro-3′,6′-dihydro-3,4′-bipyridine-1′(2′H)-carboxylate (1.3 g, 60%) as a white solid. LCMS (FA): Rt=2.16 min, m/z=348.3 (M+H).

Workup

  1. customThe reaction mixture was flushed with nitrogen gas
  2. filtrationThe reaction mixture was filtered through a Celite® pad
  3. washwashed with DCM
  4. washThe filtrate was washed with brine
  5. dry with materialdried over Na2SO4
  6. filtrationfiltered
  7. concentrationconcentrated
  8. customThe residue was purified by column chromatography

Sources & evidence

ORD record
ord-dc246d678e1745b4aa6ec86187331964
Source dataset
uspto-grants-2012_09
Patent number
US08268992B2

Reaction notes

Loading…