Pyridine, 2-(trimethylsilyl)- → Methyl [2,3'-bipyridine]-6'-carboxylate

HRID 1913154Notes

Reaction equation

HRID 1913154 reaction equation
[CH3:1][O:2][C:3]([C:5]1[CH:10]=[CH:9][C:8](Br)=[CH:7][N:6]=1)=[O:4].C[Si](C)(C)[C:14]1[CH:19]=[CH:18][CH:17]=[CH:16][N:15]=1.[F-].C([N+](CCCC)(CCCC)CCCC)CCC>CN(C)C=O.[Ag-]=O.[CH2-]C=C.[CH2-]C=C.Cl[Pd+].Cl[Pd+]>[N:15]1[CH:16]=[CH:17][CH:18]=[CH:19][C:14]=1[C:8]1[CH:7]=[N:6][C:5]([C:3]([O:2][CH3:1])=[O:4])=[CH:10][CH:9]=1

Participants

7

Reactant 3

HCID 139573Pyridine, 2-(trimethylsilyl)-HCID 2724141Tetrabutylammonium FluorideHCID 7016458Methyl 5-bromopyridine-2-carboxylate

Product 1

HCID 58494565Methyl [2,3'-bipyridine]-6'-carboxylateYield 48%

Reagents, catalysts & solvents 3

HCID 61538Palladium, di-mu-chlorobis(eta3-2-propenyl)di-CatalystHCID 178418778HCID 178418778, compoundCatalystHCID 6228DimethylformamideSolvent

Conditions

Temperature
90 °C

Procedure

This compound is synthesized as described by adaptation of the following reference: Tye et al., Tet. Lett., 2008, 49, 3939. To a stirred suspension of methyl-5-bromo-2-pyridine carboxylate (0.25 g, 1.16 mmol) and 2-(trimethylsilyl)pyridine (0.48 mL), 3.48 mmol) in anhydrous N,N-dimethyl formamide (7.5 mL) is added silver (I) oxide (0.27 g, 1.16 mmol), allyl palladium chloride dimer (21 mg, 5 mol %) and tetrabutyl ammonium fluoride (1M in THF, 0.116 mL). The reaction is heated at 90° C. for 18 h. The reaction mixture is filtered and washed with EtOAc. The filtrate is concentrated under reduced pressure. Purification by column chromatography (silica, eluent DCM, 0-2% MeOH) gives 0.12 g (48%) of methyl 2,3′-bipyridine-6′-carboxylate. m/z=215 [M++H].

Workup

  1. customThis compound is synthesized
  2. filtrationThe reaction mixture is filtered
  3. washwashed with EtOAc
  4. concentrationThe filtrate is concentrated under reduced pressure
  5. customPurification by column chromatography (silica, eluent DCM, 0-2% MeOH)

Sources & evidence

ORD record
ord-b4ceba97887044c68ce83f751d27440b
Source dataset
uspto-grants-2013_12
Patent number
US08609696B2

Reaction notes

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