Triethylamine → 4-chloro-5-trimethylsilylethynyl-7H-pyrrolo[2,3-d]pyrimidine

HRID 2059575Notes

Reaction equation

HRID 2059575 reaction equation
[Al].[Cl:2][C:3]1[C:4]2[C:11](I)=[CH:10][NH:9][C:5]=2[N:6]=[CH:7][N:8]=1.[CH3:13][Si:14]([C:17]#[CH:18])([CH3:16])[CH3:15].C(N(CC)CC)C>C1COCC1.[Cu]I.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.CN(C=O)C>[Cl:2][C:3]1[C:4]2[C:11]([C:18]#[C:17][Si:14]([CH3:16])([CH3:15])[CH3:13])=[CH:10][NH:9][C:5]=2[N:6]=[CH:7][N:8]=1

Participants

9

Reactant 4

HCID 8471TriethylamineHCID 66111TrimethylsilylacetyleneHCID 5359268AluminumHCID 148092816-Chloro-7-iodo-7-deazapurine

Product 1

HCID 112996804-chloro-5-trimethylsilylethynyl-7H-pyrrolo[2,3-d]pyrimidine

Reagents, catalysts & solvents 4

HCID 24350Copper(1+) iodide; Copper(I) iodide; Cuprous iodide; Cuprous iodide (CuI)CatalystHCID 178418397HCID 178418397, compoundCatalystHCID 6228DimethylformamideSolventHCID 8028TetrahydrofuranSolvent

Procedure

To a 250 ml round-bottomed flask, protected from light with aluminum foil, are added 4-chloro-5-iodo-7H-pyrrolo[2,3-d]pyrimidine (1.3 g, 4.6 mmol), copper(I) iodide (0.17 g, 0.93 mmol), trimethylsilylacetylene (0.96 ml, 6.97 mmol), and tetrakis(triphenylphosphine)palladium(0) (0.26 g, 0.23 mmol) dissolved in anhydrous THF (60 ml), anhydrous DMF (20 ml) and triethyl amine (0.64 ml, 4.65 mmol). The reaction mixture is stirred at room temperature under nitrogen for 16 hrs. The solvent is removed in vacuo, and the residue is dissolved in methylene chloride (250 ml). The reaction mixture is washed with water (3×50 ml), and the combined organic layer is dried over Na2SO4, and concentrated in vacuo. The crude residue is purified by flash-chromatography on silica gel and eluted with 70% EtOAc in cyclohexane. Fractions containing the desired product (TLC) are pooled and evaporated to afford 4-chloro-5-trimethylsilylethynyl-7H-pyrrolo[2,3-d]pyrimidine as a tan white solid.

Workup

  1. customTo a 250 ml round-bottomed flask, protected
  2. customThe solvent is removed in vacuo
  3. dissolutionthe residue is dissolved in methylene chloride (250 ml)
  4. washThe reaction mixture is washed with water (3×50 ml)
  5. dry with materialthe combined organic layer is dried over Na2SO4
  6. concentrationconcentrated in vacuo
  7. customThe crude residue is purified by flash-chromatography on silica gel
  8. washeluted with 70% EtOAc in cyclohexane
  9. additionFractions containing the desired product (TLC)
  10. customevaporated

Sources & evidence

ORD record
ord-e44414f067384efcb9086dcad3c2f042
Source dataset
uspto-grants-2012_10
Patent number
US08278282B2

Reaction notes

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