Tert-Butyl nitrite → Adenosine,2-bromo-2'-deoxy-(9CI)

HRID 1358696Notes

Reaction equation

HRID 1358696 reaction equation
[CH:1]1[N:9]([C@@H:10]2[O:14][C@H:13]([CH2:15][OH:16])O[CH2:11]2)[C:8]2[N:7]=[C:6](N)[N:5]=[C:4]([NH2:18])[C:3]=2[N:2]=1.[Sb](Br)(Br)[Br:20].N([O:25][C:26](C)(C)C)=O.C(#N)C.O>ClC(Cl)C.CS(C)=O.C(O)(=O)C>[Br:20][C:6]1[N:5]=[C:4]([NH2:18])[C:3]2[N:2]=[CH:1][N:9]([C:8]=2[N:7]=1)[C@@H:10]1[O:14][C@H:13]([CH2:15][OH:16])[C@@H:26]([OH:25])[CH2:11]1

Participants

7

Reactant 4

HCID 10906Tert-Butyl nitriteHCID 24615Antimony tribromideHCID 124088AmdoxovirHCID 18373917Acetonitrile--water (1/1)

Product 1

HCID 10065192Adenosine,2-bromo-2'-deoxy-(9CI)

Reagents, catalysts & solvents 2

HCID 176Acetic AcidSolventHCID 20230201dichloroethane DMSOSolvent

Conditions

Temperature
0 °C

Procedure

DAPD (2 g, 7.5 mmol) was suspended in 170 mL dichloroethane/DMSO (4:1) and cooled to 0° C. under an inert atmosphere. To this was added antimony tribromide (3.8 g, 10.5 mmol) and tert-butyl nitrite (1.85 mL, 1.6 g, 15.5 mmol) followed by stirring while allowing the reaction to warm to room temperature. Analysis by HPLC [Novapak C-18; 5% acetonitrile/water, 0.1M TEA, pH 7 with acetic acid] revealed a new peak that eluted at 5.59 minutes (a retention time that was expected for the brominated product) with concomitant loss of DAPD starting material. The reaction was stirred overnight and quenched with triethylamine. The conversion by HPLC was 26% indicating the synthesis of 2-bromo-2′-deoxyadenosine.

Workup

  1. customthe reaction
  2. temperatureto warm to room temperature
  3. washthat eluted at 5.59 minutes (a retention time that
  4. stirringThe reaction was stirred overnight
  5. customquenched with triethylamine
  6. customthe synthesis of 2-bromo-2′-deoxyadenosine

Sources & evidence

ORD record
ord-68c5885cd720466eba66ef062d0fd6aa
Source dataset
uspto-grants-2003_07
Patent number
US06596858B2

Reaction notes

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