Sodium Carbonate → tert-Butyl 4-(2-methyl-3-pyridyl)-3,6-dihydro-2H-pyridine-1-carboxylate

HRID 1775347Notes

Reaction equation

HRID 1775347 reaction equation
Br[C:2]1[C:3]([CH3:8])=[N:4][CH:5]=[CH:6][CH:7]=1.CC1(C)C(C)(C)OB([C:17]2[CH2:18][CH2:19][N:20]([C:23]([O:25][C:26]([CH3:29])([CH3:28])[CH3:27])=[O:24])[CH2:21][CH:22]=2)O1.C(=O)([O-])[O-].[Na+].[Na+]>C1COCC1.O.C(OCC)(=O)C.Cl[Pd](Cl)([P](C1C=CC=CC=1)(C1C=CC=CC=1)C1C=CC=CC=1)[P](C1C=CC=CC=1)(C1C=CC=CC=1)C1C=CC=CC=1>[CH3:8][C:3]1[C:2]([C:17]2[CH2:22][CH2:21][N:20]([C:23]([O:25][C:26]([CH3:29])([CH3:28])[CH3:27])=[O:24])[CH2:19][CH:18]=2)=[CH:7][CH:6]=[CH:5][N:4]=1

Participants

8

Reactant 3

HCID 10340Sodium CarbonateHCID 12010033-Bromo-2-methylpyridineHCID 4642098Tert-butyl 4-(4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl)-1,2,3,6-tetrahydropyridine-1-carboxylate

Product 1

HCID 121257689tert-Butyl 4-(2-methyl-3-pyridyl)-3,6-dihydro-2H-pyridine-1-carboxylateYield 76%

Reagents, catalysts & solvents 4

HCID 178418476HCID 178418476, compoundCatalystHCID 962WaterSolventHCID 8028TetrahydrofuranSolventHCID 8857Ethyl AcetateSolvent

Procedure

3-Bromo-2-methylpyridine (172 mg, 1 mmol) and tert-butyl 4-(4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl)-3,6-dihydro-2H-pyridine-1-carboxylate (309 mg, 1 mmol) were dissolved in THF (10 ml) and combined with a solution of sodium carbonate (425 mg, 4 mmol) in water (1 ml). The mixture was purged with argon, PdCl2(PPh3)2 (35 mg, 0.05 mmol) was added and the mixture was stirred under reflux for three days, diluted with ethyl acetate (30 ml), the phases were separated and the organic layer was washed with brine and dried (sodium sulfate). After concentration under reduced pressure the residue was purified with column chromatography (silica, gradient of 0 to 30% ethyl acetate in DCM) to yield 209 mg (0.76 mmol, yield 76%) MS (multi-mode) m/z=275.2 [M+1]+.

Workup

  1. additionwas added
  2. temperatureunder reflux for three days
  3. customthe phases were separated
  4. washthe organic layer was washed with brine
  5. dry with materialdried (sodium sulfate)
  6. concentrationAfter concentration under reduced pressure the residue
  7. customwas purified with column chromatography (silica, gradient of 0 to 30% ethyl acetate in DCM)
  8. customto yield 209 mg (0.76 mmol, yield 76%)

Sources & evidence

ORD record
ord-fedfbd136a3e43d698a973c02bbbc755
Source dataset
uspto-grants-2016_02
Patent number
US09260441B2

Reaction notes

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