Ethyl Acetate → 2-Fluoro-3-(1,4-dioxaspiro[4.5]dec-7-en-8-yl)pyridine

HRID 410240Notes

Reaction equation

HRID 410240 reaction equation
FC(F)(F)S(O[C:7]1[CH2:16][CH2:15][C:10]2([O:14][CH2:13][CH2:12][O:11]2)[CH2:9][CH:8]=1)(=O)=O.[F:19][C:20]1[C:25](B(O)O)=[CH:24][CH:23]=[CH:22][N:21]=1.C(=O)([O-])[O-].[Na+].[Na+].C(OCC)(=O)C>COCCOC.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.[Pd]>[F:19][C:20]1[C:25]([C:7]2[CH2:16][CH2:15][C:10]3([O:11][CH2:12][CH2:13][O:14]3)[CH2:9][CH:8]=2)=[CH:24][CH:23]=[CH:22][N:21]=1

Participants

7

Reactant 4

HCID 8857Ethyl AcetateHCID 10340Sodium CarbonateHCID 27832702-Fluoropyridine-3-boronic acidHCID 114830861,4-Dioxaspiro[4.5]dec-7-en-8-yl trifluoromethanesulfonate

Product 1

HCID 576066882-Fluoro-3-(1,4-dioxaspiro[4.5]dec-7-en-8-yl)pyridine

Reagents, catalysts & solvents 2

HCID 11979704Tetrakis(triphenylphosphine)palladiumCatalystHCID 80711,2-DimethoxyethaneSolvent

Conditions

Temperature
85 °C

Procedure

To a mixture of 1,4-dioxaspiro[4.5]dec-7-en-8-yl trifluoromethanesulfonate (10.2 g, 35.4 mmol) and 2-fluoropyridin-3-ylboronic acid (5.00 g, 35.5 mmol) in 1,2-dimethoxyethane (200 mL) and aqueous sodium carbonate (53.2 mL, 106 mmol, 2N) under argon atmosphere was added palladium tetrakis(triphenylphosphine) (1.23 g, 1.06 mmol). The mixture was heated and stirred at 85° C. for 1 h., then cooled to room temperature. Ethyl acetate was added and the mixture was washed with water, saturated sodium chloride, dried over anhydrous magnesium sulfate, filtered, and concentrated in vacuo. The resulting oil was purified by silica gel chromatography to give 2-fluoro-3-(1,4-dioxaspiro[4.5]dec-7-en-8-yl)pyridine. MS (ESI, pos. ion) m/z: 236.1 (M+1).

Workup

  1. temperatureThe mixture was heated
  2. temperaturecooled to room temperature
  3. washthe mixture was washed with water, saturated sodium chloride
  4. dry with materialdried over anhydrous magnesium sulfate
  5. filtrationfiltered
  6. concentrationconcentrated in vacuo
  7. customThe resulting oil was purified by silica gel chromatography

Sources & evidence

ORD record
ord-adce9c92893c4828a2710cc2c257a06a
Source dataset
uspto-grants-2014_06
Patent number
US08759532B2

Reaction notes

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