tert-butyl N-(prop-2-yn-1-yl)carbamate → HCID 70881450, compound

HRID 1892213Notes

Reaction equation

HRID 1892213 reaction equation
Br[C:2]1[CH:3]=[C:4]([N+:9]([O-:11])=[O:10])[C:5]([CH3:8])=[N:6][CH:7]=1.[CH2:12]([NH:15][C:16](=[O:22])[O:17][C:18]([CH3:21])([CH3:20])[CH3:19])[C:13]#[CH:14]>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:18]([O:17][C:16](=[O:22])[NH:15][CH2:12][C:13]#[C:14][C:2]1[CH:7]=[N:6][C:5]([CH3:8])=[C:4]([N+:9]([O-:11])=[O:10])[CH:3]=1)([CH3:21])([CH3:20])[CH3:19]

Participants

5

Reactant 2

HCID 11073648tert-butyl N-(prop-2-yn-1-yl)carbamateHCID 250672665-Bromo-2-methyl-3-nitropyridine

Product 1

HCID 70881450HCID 70881450, compoundYield 79.3%

Reagents, catalysts & solvents 2

HCID 24350Copper(1+) iodide; Copper(I) iodide; Cuprous iodide; Cuprous iodide (CuI)CatalystHCID 178418476HCID 178418476, compoundCatalyst

Conditions

Temperature
70 °C

Procedure

To a solution of 5-bromo-2-methyl-3-nitropyridine (2.81 g, 12.9 mmol) in TEA (25 mL) was added tert-butyl prop-2-yn-1-ylcarbamate (2.58 g, 16.6 mmol). The solution was degassed with argon. To the reaction mixture were added bis(triphenylphosphine)palladium(II) chloride (0.18 g, 0.26 mmol) and copper(I) iodide (0.098 g, 0.52 mmol). The reaction mixture was allowed to stir at 70° C. for 2.5 h and was then concentrated and diluted with EtOAc (100 mL). The mixture was filtered over a pad of Celite® and the resulting filtrate was washed with sat. aq. NaHCO3 (100 mL). The organic solution was dried over MgSO4, filtered and concentrated. The residue was purified by column chromatography to give tert-butyl[3-(6-methyl-5-nitropyridin-3-yl)prop-2-yn-1-yl]carbamate (2.98 g, 79%) as a yellow solid. LCMS (FA): Rt=1.81 min, m/z=292.0 (M+H).

Workup

  1. customThe solution was degassed with argon
  2. concentrationwas then concentrated
  3. additiondiluted with EtOAc (100 mL)
  4. filtrationThe mixture was filtered over a pad of Celite®
  5. washthe resulting filtrate was washed with sat. aq. NaHCO3 (100 mL)
  6. dry with materialThe organic solution was dried over MgSO4
  7. filtrationfiltered
  8. concentrationconcentrated
  9. customThe residue was purified by column chromatography

Sources & evidence

ORD record
ord-3723b5e38fd34dd59a4bfe3c070f664a
Source dataset
uspto-grants-2013_08
Patent number
US08507667B2

Reaction notes

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