Propyne → (3-Prop-1-ynylpyridin-4-yl)carbamic acid tert-butyl ester

HRID 400608Notes

Reaction equation

HRID 400608 reaction equation
[CH:1]#[C:2][CH3:3].[C:4]([O:8][C:9](=[O:18])[NH:10][C:11]1[CH:16]=[CH:15][N:14]=[CH:13][C:12]=1I)([CH3:7])([CH3:6])[CH3:5].C(OCC)(=O)C.[Cl-].[NH4+]>CN(C=O)C.C(N(CC)CC)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.[Cu]I>[C:4]([O:8][C:9](=[O:18])[NH:10][C:11]1[CH:16]=[CH:15][N:14]=[CH:13][C:12]=1[C:1]#[C:2][CH3:3])([CH3:7])([CH3:6])[CH3:5]

Participants

9

Reactant 4

HCID 6335PropyneHCID 8857Ethyl AcetateHCID 25517Ammonium ChlorideHCID 10903275(3-Iodo-pyridin-4-yl)-carbamic acid tert-butyl ester

Product 1

HCID 11031741(3-Prop-1-ynylpyridin-4-yl)carbamic acid tert-butyl esterYield 98%

Reagents, catalysts & solvents 4

HCID 24350Copper(1+) iodide; Copper(I) iodide; Cuprous iodide; Cuprous iodide (CuI)CatalystHCID 178418476HCID 178418476, compoundCatalystHCID 6228DimethylformamideSolventHCID 8471TriethylamineSolvent

Procedure

Propyne (6.3 mL, 124 mmol) was condensed in a pressure tube at −78° C. A solution of (3-iodopyridin-4-yl)carbamic acid tert-butyl ester (7.98 g, 24.9 mmol) in 15 mL of DMF, 60 mL of triethylamine, dichlorobis(triphenylphosphine)palladium (II) (877 mg, 1.25 mmol), and CuI (472 mg, 2.49 mmol) were added, and the tube was sealed and stirred at room temperature overnight. 200 mL of ethyl acetate and 100 mL of saturated aqueous ammonium chloride solution were added, the phases were separated and the aqueous layer was extracted with three 100 mL portions of ethyl acetate. The combined organic layers were dried over magnesium sulfate, filtered, and concentrated in vacuo. Chromatography on SiO2 (25% to 40% ethyl acetate in hexanes, gradient) afforded 5.65 g of (3-prop-1-ynylpyridin-4-yl)carbamic acid tert-butyl ester (98% yield).

Workup

  1. customcondensed in a pressure tube at −78° C
  2. customthe tube was sealed
  3. customthe phases were separated
  4. extractionthe aqueous layer was extracted with three 100 mL portions of ethyl acetate
  5. dry with materialThe combined organic layers were dried over magnesium sulfate
  6. filtrationfiltered
  7. concentrationconcentrated in vacuo

Sources & evidence

ORD record
ord-1651c747b4ee4cd181fbb69cce7c9731
Source dataset
uspto-grants-2014_06
Patent number
US08741897B2

Reaction notes

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