4-(Tri-n-butylstannyl)pyridine → HCID 24937863, compound

HRID 391716Notes

Reaction equation

HRID 391716 reaction equation
[O:1]=[C:2]1[CH2:11][N:10]([C:12]2[CH:17]=[CH:16][CH:15]=[CH:14][CH:13]=2)[C:9]2[N:8]=[C:7]([C:18]3[CH:23]=[CH:22][N:21]=[CH:20][CH:19]=3)[N:6]=[C:5]([C:24]([O:26]CC)=O)[C:4]=2[NH:3]1.ClC1N=C(C(OCC)=O)C2NC(=O)CN(C3C=CC=CC=3)C=2[N:31]=1.C([Sn](CCCC)(CCCC)C1C=CN=CC=1)CCC>CN(C=O)C.C(Cl)Cl.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>[O:1]=[C:2]1[CH2:11][N:10]([C:12]2[CH:17]=[CH:16][CH:15]=[CH:14][CH:13]=2)[C:9]2[N:8]=[C:7]([C:18]3[CH:19]=[CH:20][N:21]=[CH:22][CH:23]=3)[N:6]=[C:5]([C:24]([NH2:31])=[O:26])[C:4]=2[NH:3]1

Participants

7

Reactant 3

HCID 27373184-(Tri-n-butylstannyl)pyridineHCID 57474562HCID 57474562, compoundHCID 57474870HCID 57474870, compound

Product 1

HCID 24937863HCID 24937863, compoundYield 50%

Reagents, catalysts & solvents 3

HCID 178418476HCID 178418476, compoundCatalystHCID 6228DimethylformamideSolventHCID 6344DichloromethaneSolvent

Conditions

Temperature
120 °C

Procedure

Ethyl 6-oxo-8-phenyl-2-(pyridin-4-yl)-5,6,7,8-tetrahydropteridine-4-carboxylate. To a solution of ethyl 2-chloro-6-oxo-8-phenyl-5,6,7,8-tetrahydropteridine-4-carboxylate (0.160 g, 0.48 mmol) in anhydrous DMF (6.7 mL) was added 4-(tributylstannyl)pyridine (0.884 g, 2.40 mmol), and dichlorobis(triphenylphosphine)palladium(II) (0.170 g, 0.24 mmol). The solution was purged with nitrogen then heated in a Biotage Emrys Optimizer microwave reactor for 30 min at 120° C. The volatiles were evaporated and the resulting residue was purified by chromatography on a normal phase silica gel column (1-10% methanol in dichloromethane). Fractions containing product were combined and the solvent evaporated. The material was re-purified using reverse-phase preparatory HPLC (10-70% acetonitrile+0.1% TFA in H2O+0.1% TFA, over 30 min). Fractions containing the desired material were combined and concentrated under reduced pressure to afford a residue. The residue was dissolved in methylene chloride (100 mL) which was washed with aqueous potassium carbonate solution (saturated, 10 mL) and dried over sodium sulfate. The organic phase was concentrated and the resulting solid was dried under high vacuum at 60° C. to afford the title compound (0.090 g, 0.24 mmol, 50% yield). MS (ESI) m/z 376.4 [M+1]+.

Workup

  1. customThe solution was purged with nitrogen
  2. customThe volatiles were evaporated
  3. customthe resulting residue was purified by chromatography on a normal phase silica gel column (1-10% methanol in dichloromethane)
  4. additionFractions containing product
  5. customthe solvent evaporated
  6. customThe material was re-purified
  7. customreverse-phase preparatory HPLC (10-70% acetonitrile+0.1% TFA in H2O+0.1% TFA, over 30 min)
  8. additionFractions containing the desired material
  9. concentrationconcentrated under reduced pressure
  10. customto afford a residue
  11. washwas washed with aqueous potassium carbonate solution (saturated, 10 mL)
  12. dry with materialdried over sodium sulfate
  13. concentrationThe organic phase was concentrated
  14. customthe resulting solid was dried under high vacuum at 60° C.

Sources & evidence

ORD record
ord-400b7acaf53d44969b56f49d0aa75a5e
Source dataset
uspto-grants-2013_02
Patent number
US08383634B2

Reaction notes

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