Sodium Thiosulfate → 7-[(1S)-2-{[tert-Butyl(dimethyl)silyl]oxy}-1-methylethyl]-5-iodo-7H-pyrrolo[2,3-d]pyrimidine

HRID 82145Notes

Reaction equation

HRID 82145 reaction equation
[I:1]N1C(=O)CCC1=O.[Si:9]([O:16][CH2:17][C@@H:18]([N:20]1[C:24]2[N:25]=[CH:26][N:27]=[CH:28][C:23]=2[CH:22]=[CH:21]1)[CH3:19])([C:12]([CH3:15])([CH3:14])[CH3:13])([CH3:11])[CH3:10].S([O-])([O-])(=O)=S.[Na+].[Na+]>C(#N)C>[Si:9]([O:16][CH2:17][C@@H:18]([N:20]1[C:24]2[N:25]=[CH:26][N:27]=[CH:28][C:23]=2[C:22]([I:1])=[CH:21]1)[CH3:19])([C:12]([CH3:13])([CH3:14])[CH3:15])([CH3:10])[CH3:11]

Participants

5

Reactant 3

HCID 24477Sodium ThiosulfateHCID 120273N-IodosuccinimideHCID 708176697-[(1S)-2-{[tert-Butyl(dimethyl)silyl]oxy}-1-methylethyl]-7H-pyrrolo[2,3-d]pyrimidine

Product 1

HCID 708175957-[(1S)-2-{[tert-Butyl(dimethyl)silyl]oxy}-1-methylethyl]-5-iodo-7H-pyrrolo[2,3-d]pyrimidineYield 66%

Reagents, catalysts & solvents 1

HCID 6342AcetonitrileSolvent

Procedure

N-Iodosuccinimide (124 g, 553 mmol) was added to 7-[(1S)-2-{[tert-butyl(dimethyl)silyl]oxy}-1-methylethyl]-7H-pyrrolo[2,3-d]pyrimidine (153.4 g, 526 mmol) (see Preparation 8) in acetonitrile (700 mL). The mixture was stirred at room temperature for 16 hours then saturated aqueous sodium thiosulfate (700 mL) was added. The mixture was extracted with EtOAc (800 mL) then the organic extract was dried over magnesium sulfate and evaporated in vacuo. The crude material was purified by column chromatography on silica gel (gradient of pentane:EtOAc 90:10 to 80:20) to afford the title compound as a yellow solid in 66% yield, 145 g. 1H NMR (400 MHz, CDCl3) δ: −0.90 (d, 6H) 0.80 (s, 9H) 1.58 (d, 3H) 3.84 (m, 2H) 5.07 (m, 1H) 7.48 (s, 1H) 8.73 (s, 1H) 8.86 (s, 1H).

Workup

  1. extractionThe mixture was extracted with EtOAc (800 mL)
  2. extractionthe organic extract
  3. dry with materialwas dried over magnesium sulfate
  4. customevaporated in vacuo
  5. customThe crude material was purified by column chromatography on silica gel (gradient of pentane:EtOAc 90:10 to 80:20)

Sources & evidence

ORD record
ord-73c9876118604053ac3c0cfdab76386f
Source dataset
uspto-grants-2014_09
Patent number
US08846698B2

Reaction notes

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