2-(Tributylstannyl)pyridine → HCID 66977115, compound

HRID 712356Notes

Reaction equation

HRID 712356 reaction equation
[NH2:1][C:2]1[C:7]([N+:8]([O-:10])=[O:9])=[CH:6][C:5]([C:11]2[CH:12]=[N:13][C:14]([N:17]3[CH2:22][CH2:21][C:20]([CH2:28][CH3:29])([C:23]([O:25][CH2:26][CH3:27])=[O:24])[CH2:19][CH2:18]3)=[N:15][CH:16]=2)=[CH:4][C:3]=1Br.C([Sn](CCCC)(CCCC)[C:36]1[CH:41]=[CH:40][CH:39]=[CH:38][N:37]=1)CCC>CN(C=O)C.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>[NH2:1][C:2]1[C:3]([C:36]2[CH:41]=[CH:40][CH:39]=[CH:38][N:37]=2)=[CH:4][C:5]([C:11]2[CH:16]=[N:15][C:14]([N:17]3[CH2:18][CH2:19][C:20]([CH2:28][CH3:29])([C:23]([O:25][CH2:26][CH3:27])=[O:24])[CH2:21][CH2:22]3)=[N:13][CH:12]=2)=[CH:6][C:7]=1[N+:8]([O-:10])=[O:9]

Participants

5

Reactant 2

HCID 6077842-(Tributylstannyl)pyridineHCID 66977175HCID 66977175, compound

Product 1

HCID 66977115HCID 66977115, compoundYield 47.6%

Reagents, catalysts & solvents 2

HCID 178418397HCID 178418397, compoundCatalystHCID 6228DimethylformamideSolvent

Conditions

Temperature
120 °C

Procedure

To a solution of ethyl 1-(5-(4-amino-3-bromo-5-nitrophenyl)pyrimidin-2-yl)-4-ethylpiperidine-4-carboxylate (1.5 g, 3.14 mmol) in DMF (10.0 mL) was added 2-(tributylstannyl)pyridine (1.73 g, 4.72 mmol) and the mixture degassed by purging N2 for 15 min followed by addition of tetrakis(triphenylphosphine)palladium(0) (0.36 g, 0.314 mmol). The reaction mixture was again degassed for 10 min then heated up to 120° C. for 5 h. After completion of reaction, 100 mL ice-cold water was added, extracted with EtOAc (4×100 mL) and the combined organic layer washed with ice-cold water, brine solution respectively, dried over Na2SO4, filtered and evaporated under reduced pressure. The crude residue was purified over neutral alumina using 15% EtOAc:Hexane to obtain the desired product (0.712 g, 47%). 1H NMR (CDCl3): δ 8.68-8.69 (m, 1H), 8.63 (s, 2H), 8.38 (s, 1H), 7.89 (s, 1H), 7.84 (s, 1H), 7.69 (d, J=8.4 Hz, 1H), 7.34-7.36 (m, 1H), 4.65-4.67 (m, 2H), 4.20-4.22 (m, 2H), 3.21-3.25 (m, 2H), 2.30-2.34 (m, 2H), 1.58-1.60 (m, 2H), 1.44-1.46 (m, 2H), 1.30 (t, J=7.20 Hz, 3H) and 0.86 (t, J=7.60 Hz, 3H). MS: 477.44 [M+H]+.

Workup

  1. customthe mixture degassed
  2. customby purging N2 for 15 min
  3. customThe reaction mixture was again degassed for 10 min
  4. customAfter completion of reaction, 100 mL ice-cold water
  5. additionwas added
  6. extractionextracted with EtOAc (4×100 mL)
  7. washthe combined organic layer washed with ice-cold water, brine solution respectively
  8. dry with materialdried over Na2SO4
  9. filtrationfiltered
  10. customevaporated under reduced pressure
  11. customThe crude residue was purified over neutral alumina using 15% EtOAc

Sources & evidence

ORD record
ord-79fa5701831849dc8e2ed1d1c43dff1e
Source dataset
uspto-grants-2015_11
Patent number
US09181234B2

Reaction notes

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