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

HRID 1892195Notes

Reaction equation

HRID 1892195 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-c67a6085099e43448be329ba75b7750e
Source dataset
uspto-grants-2013_08
Patent number
US08507667B2

Reaction notes

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