Potassium Phosphate, Tribasic → Methyl 2-methoxy-2'-methyl-3,4'-bipyridine-6-carboxylate

HRID 2178682Notes

Reaction equation

HRID 2178682 reaction equation
Br[C:2]1[CH:7]=[CH:6][N:5]=[C:4]([CH3:8])[CH:3]=1.[CH3:9][O:10][C:11]1[N:16]=[C:15]([C:17]([O:19][CH3:20])=[O:18])[CH:14]=[CH:13][C:12]=1B1OC(C)(C)C(C)(C)O1.P([O-])([O-])([O-])=O.[K+].[K+].[K+]>C1C=CC([P]([Pd]([P](C2C=CC=CC=2)(C2C=CC=CC=2)C2C=CC=CC=2)([P](C2C=CC=CC=2)(C2C=CC=CC=2)C2C=CC=CC=2)[P](C2C=CC=CC=2)(C2C=CC=CC=2)C2C=CC=CC=2)(C2C=CC=CC=2)C2C=CC=CC=2)=CC=1>[CH3:9][O:10][C:11]1[C:12]([C:2]2[CH:7]=[CH:6][N:5]=[C:4]([CH3:8])[CH:3]=2)=[CH:13][CH:14]=[C:15]([C:17]([O:19][CH3:20])=[O:18])[N:16]=1

Participants

5

Reactant 3

HCID 62657Potassium Phosphate, TribasicHCID 27628354-Bromo-2-methylpyridineHCID 68380502Methyl 6-methoxy-5-(4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl)picolinate

Product 1

HCID 68380339Methyl 2-methoxy-2'-methyl-3,4'-bipyridine-6-carboxylate

Reagents, catalysts & solvents 1

HCID 178418397HCID 178418397, compoundCatalyst

Conditions

Temperature
80 °C

Procedure

Degassed 1,2-dimethoxyethane (60 mL) and water (0.5 mL) were added to a flask charged with 4-bromo-2-methylpyridine (1.20 g, 6.98 mmol), methyl 6-methoxy-5-(4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl)pyridine-2-carboxylate (C31) (3.07 g, 10.5 mmol), potassium phosphate (4.44 g, 20.9 mmol), and tetrakis(triphenylphosphine)palladium(0) (0.81 g, 0.70 mmol). The mixture was heated to 80° C. for 18 hours, then cooled to room temperature and concentrated in vacuo. Silica gel chromatography (Eluant: ethyl acetate) provided a solid, which was triturated twice with a 1:5 mixture of ethyl acetate and heptane to provide the title compound as a white solid. Yield: 1.68 g, 6.50 mmol, 93%. LCMS m/z 259.1 (M+1). 1H NMR (400 MHz, CDCl3) δ 2.63 (s, 3H), 4.00 (s, 3H), 4.09 (s, 3H), 7.32 (br d, J=5.5 Hz, 1H), 7.36 (br s, 1H), 7.79 (AB quartet, JAB=7.3 Hz, ΔνAB=24.1 Hz, 2H), 8.57 (d, J=5.0 Hz, 1H).

Workup

  1. customDegassed 1,2-dimethoxyethane (60 mL) and water (0.5 mL)
  2. additionwere added to a flask
  3. temperaturecooled to room temperature
  4. concentrationconcentrated in vacuo
  5. customSilica gel chromatography (Eluant: ethyl acetate) provided a solid, which
  6. customwas triturated twice with a 1:5 mixture of ethyl acetate and heptane

Sources & evidence

ORD record
ord-4cfd23775e2a44f38a9f0f02ea51d047
Source dataset
uspto-grants-2015_06
Patent number
US09067934B2

Reaction notes

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