Diisopropylethylamine → 5-Allylpyrazin-2-amine

HRID 720008Notes

Reaction equation

HRID 720008 reaction equation
[NH2:1][C:2]1[CH:7]=[N:6][C:5](Br)=[CH:4][N:3]=1.[CH2:9]([Sn](CCCC)(CCCC)CCCC)[CH:10]=[CH2:11].[Cl-].[Li+].C(N(CC)C(C)C)(C)C.[F-].[K+]>CN(C)C=O.C1C=CC([P]([Pd]([P](C2C=CC=CC=2)(C2C=CC=CC=2)C2C=CC=CC=2)([P](C2C=CC=CC=2)(C2C=CC=CC=2)C2C=CC=CC=2)[P](C2C=CC=CC=2)(C2C=CC=CC=2)C2C=CC=CC=2)(C2C=CC=CC=2)C2C=CC=CC=2)=CC=1.O>[CH2:11]([C:5]1[N:6]=[CH:7][C:2]([NH2:1])=[N:3][CH:4]=1)[CH:10]=[CH2:9]

Participants

9

Reactant 5

HCID 81531DiisopropylethylamineHCID 90628AllyltributylstannaneHCID 433294Lithium ChlorideHCID 522689Potassium FluorideHCID 5995392-Amino-5-bromopyrazine

Product 1

HCID 218973655-Allylpyrazin-2-amineYield 48.7%

Reagents, catalysts & solvents 3

HCID 178418397HCID 178418397, compoundCatalystHCID 962WaterSolventHCID 6228DimethylformamideSolvent

Conditions

Temperature
120 °C

Procedure

A mixture of 2-amino-5-bromopyrazine (1.00 g, 5.746 mmol), tetrakis(triphenylphosphine)palladium(0) (132 mg, 0.114 mmol), allyltri-n-butyltin (2.2 mL, 7.096 mmol), lithium chloride (875.0 mg, 20.64 mmol) and N,N-diisopropylethylamine (2.6 mL, 14.93 mmol) in N,N-dimethylformamide (29 mL) was stirred at 120° C. for 45 min. The reaction mixture was cooled to 25° C. and then treated with a saturated aqueous potassium fluoride solution (20 mL). The mixture was stirred for 3 h, treated with a solution of water and a saturated aqueous sodium chloride solution, and extracted with ethyl acetate. The combined organic layers were dried over anhydrous sodium sulfate, filtered, and concentrated in vacuo. Biotage chromatography (FLASH 40L, Silica, 1/1 hexanes/ethyl acetate) afforded 5-allyl-pyrazin-2-ylamine (378.2 mg, 48.7%) as a yellow solid: LRMS for C7H9N3 (M+H)+ at m/z=136.

Workup

  1. temperatureThe reaction mixture was cooled to 25° C.
  2. stirringThe mixture was stirred for 3 h
  3. extractiona saturated aqueous sodium chloride solution, and extracted with ethyl acetate
  4. dry with materialThe combined organic layers were dried over anhydrous sodium sulfate
  5. filtrationfiltered
  6. concentrationconcentrated in vacuo

Sources & evidence

ORD record
ord-22fdde7b365142a5a1c65e27638e55fd
Source dataset
uspto-grants-2006_11
Patent number
US07132425B2

Reaction notes

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