Diiodomethane → 6-Chloro-2-iodo-9-((2-(trimethylsilyl)ethoxy)methyl)-9H-purine

HRID 1024075Notes

Reaction equation

HRID 1024075 reaction equation
[Cl:1][C:2]1[N:10]=[C:9](N)[N:8]=[C:7]2[C:3]=1[N:4]=[CH:5][N:6]2[CH2:12][O:13][CH2:14][CH2:15][Si:16]([CH3:19])([CH3:18])[CH3:17].C(I)[I:21].N(OCCC(C)C)=O>C1COCC1.[Cu]I>[Cl:1][C:2]1[N:10]=[C:9]([I:21])[N:8]=[C:7]2[C:3]=1[N:4]=[CH:5][N:6]2[CH2:12][O:13][CH2:14][CH2:15][Si:16]([CH3:19])([CH3:18])[CH3:17]

Participants

6

Reactant 3

HCID 6346DiiodomethaneHCID 8053Isoamyl NitriteHCID 866841516-Chloro-9-((2-(trimethylsilyl)ethoxy)methyl)-9H-purin-2-amine

Product 1

HCID 600594836-Chloro-2-iodo-9-((2-(trimethylsilyl)ethoxy)methyl)-9H-purineYield 49.2%

Reagents, catalysts & solvents 2

HCID 24350Copper(1+) iodide; Copper(I) iodide; Cuprous iodide; Cuprous iodide (CuI)CatalystHCID 8028TetrahydrofuranSolvent

Procedure

To a mixture of 117a (2.99 g, 10.0 mmol), CH2I2 (4.0 ml, 51.0 mmol), and CuI (1.91 g, 10.0 mmol) in THF was added isoamyl nitrite (4.0 mL, 30.0 mmol). The mixture was heated at reflux for 1.0 h and cooled to room temperature. The reaction mixture was partitioned between ethyl acetate and 1N aqueous HCl solution. The organic phase was washed with saturated aqueous NH4Cl, dried over Na2SO4, and concentrated under reduced pressure. The residue was purified by silica-gel column chromatography eluting with 3:1 petroleum ether/ethyl acetate to afford 117b (2.02 g, 49%) as a yellow solid. MS-ESI: [M+H]+ 411.0

Workup

  1. temperatureThe mixture was heated
  2. temperatureat reflux for 1.0 h
  3. customThe reaction mixture was partitioned between ethyl acetate and 1N aqueous HCl solution
  4. washThe organic phase was washed with saturated aqueous NH4Cl
  5. dry with materialdried over Na2SO4
  6. concentrationconcentrated under reduced pressure
  7. customThe residue was purified by silica-gel column chromatography
  8. washeluting with 3:1 petroleum ether/ethyl acetate

Sources & evidence

ORD record
ord-1f8bdc5a20db418eb1b220f422f47f4d
Source dataset
uspto-grants-2014_05
Patent number
US08722676B2

Reaction notes

Loading…