Trimethyl-2-propynylsilane → 5-Bromo-3-(3-trimethylsilanyl-prop-1-ynyl)-pyrazin-2-ylamine

HRID 905985Notes

Reaction equation

HRID 905985 reaction equation
Br[C:2]1[C:3]([NH2:9])=[N:4][CH:5]=[C:6]([Br:8])[N:7]=1.[CH3:10][Si:11]([CH3:16])([CH3:15])[CH2:12][C:13]#[CH:14]>C1COCC1.CCOC(C)=O.[Cu]I>[Br:8][C:6]1[N:7]=[C:2]([C:14]#[C:13][CH2:12][Si:11]([CH3:16])([CH3:15])[CH3:10])[C:3]([NH2:9])=[N:4][CH:5]=1

Participants

6

Reactant 2

HCID 83378Trimethyl-2-propynylsilaneHCID 6200042-Amino-3,5-dibromopyrazine

Product 1

HCID 866423045-Bromo-3-(3-trimethylsilanyl-prop-1-ynyl)-pyrazin-2-ylamineYield 87.2%

Reagents, catalysts & solvents 3

HCID 24350Copper(1+) iodide; Copper(I) iodide; Cuprous iodide; Cuprous iodide (CuI)CatalystHCID 8028TetrahydrofuranSolventHCID 8857Ethyl AcetateSolvent

Procedure

3,5-Dibromo-pyrazin-2-ylamine (1.70 g, 6.70 mmol), TEA (1.1 mL, 8.04 mmol), PdCl2(PPh3)4 (28 mg, 0.040 mmol), and CuI (15 mg, 0.080 mmol) were dissolved in THF (17 mL), cooled to RT and Trimethyl-prop-2-ynyl-silane (1.0 mL, 6.7 mmol) was added at 0° C., allowed to warm up to RT and stirred overnight. The reaction mixture was diluted with EtOAc, washed with H2O and saturated aqueous NaHCO3, dried (MgSO4) and concentrated, and purified by SiO2 chromatography (80 g SiO2, hexanes/EtOAc 0-35% EtOAc) to give 1.66 g of 5-bromo-3-(3-trimethylsilanyl-prop-1-ynyl)-pyrazin-2-ylamine as a yellow semi-solid contaminated by starting material (87% yield, 66% purity).

Workup

  1. temperatureto warm up to RT
  2. washwashed with H2O and saturated aqueous NaHCO3
  3. dry with materialdried (MgSO4)
  4. concentrationconcentrated
  5. custompurified by SiO2 chromatography (80 g SiO2, hexanes/EtOAc 0-35% EtOAc)

Sources & evidence

ORD record
ord-e6cbde8d04c7467f824533ee652c141d
Source dataset
uspto-grants-2011_09
Patent number
US08012974B2

Reaction notes

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