Triethylamine → Methyl 5-formylpyridine-3-carboxylate

HRID 507148Notes

Reaction equation

HRID 507148 reaction equation
[CH3:1][O:2][C:3](=[O:11])[C:4]1[CH:9]=C(Br)[CH:7]=[N:6][CH:5]=1.C([SiH]([CH2:17][CH3:18])CC)C.C(N(CC)CC)C.[C]=[O:27]>C(#N)C.C1(P([Pd-4](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)C=CC=CC=1>[CH3:1][O:2][C:3](=[O:11])[C:4]1[CH:9]=[C:18]([CH:17]=[O:27])[CH:7]=[N:6][CH:5]=1

Participants

7

Reactant 4

HCID 8471TriethylamineHCID 12052TriethylsilaneHCID 699336Methyl 5-bromopyridine-3-carboxylateHCID 178418416HCID 178418416, compound

Product 1

HCID 19744729Methyl 5-formylpyridine-3-carboxylateYield 15%

Reagents, catalysts & solvents 2

HCID 178420553HCID 178420553, compoundCatalystHCID 6342AcetonitrileSolvent

Conditions

Temperature
60 °C

Procedure

Subject a mixture of methyl-5-bromonicotinate (1.0 g, 4.63 mmol), triethylsilane (0.807 g, 6.94 mmol), tetrakis(triphenylphosphino)palladium (0) (0.531 g, 0.460 mmol), and triethylamine (1.03 g, 10.18 mmol) in acetonitrile (10 mL) to an atmosphere of carbon monoxide gas (20 psi) heated at 60° C. for 5 h. Cool the reaction to room temperature and then absorb directly onto silica gel. Purify the residue by chromatography over silica gel, eluting with hexanes/ethyl acetate (80:20), to provide the title compound as an oil (0.114 g, 15%). 1H NMR (CDCl3, 300 MHz) δ 3.90 (s, 3H), 7.35-7.50 (m, 1H), 8.32-8.42 (m, 1H), 8.77-8.90 (m, 1H), 9.23 (s, 1H); TLC Rf=0.37 (4:1 Hexanes/Ethyl Acetate).

Workup

  1. temperatureCool
  2. customthe reaction to room temperature
  3. customabsorb directly onto silica gel
  4. customPurify the residue by chromatography over silica gel
  5. washeluting with hexanes/ethyl acetate (80:20)

Sources & evidence

ORD record
ord-267fbabb51594f288bbfbb93d2506d25
Source dataset
uspto-grants-2010_08
Patent number
US07786108B2

Reaction notes

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