Imidazole → HCID 68469741, compound

HRID 1889610Notes

Reaction equation

HRID 1889610 reaction equation
N1(O[C:11]2[C:12]3[N:13]=[CH:14][N:15]([C:38]=3[N:39]=[CH:40][N:41]=2)[C@@H:16]2[O:37][C@H:27]([CH2:28][O:29][Si:30]([C:33]([CH3:36])([CH3:35])[CH3:34])([CH3:32])[CH3:31])[C@@H:18]([O:19][Si:20]([C:23]([CH3:26])([CH3:25])[CH3:24])([CH3:22])[CH3:21])[CH2:17]2)C2C=CC=CC=2N=N1.C([O-])([O-])=O.[Cs+].[Cs+].[NH:48]1[CH:52]=[CH:51][N:50]=[CH:49]1>COCCOC>[N:48]1([C:11]2[N:41]=[CH:40][N:39]=[C:38]3[C:12]=2[N:13]=[CH:14][N:15]3[C@@H:16]2[O:37][C@H:27]([CH2:28][O:29][Si:30]([C:33]([CH3:36])([CH3:35])[CH3:34])([CH3:31])[CH3:32])[C@@H:18]([O:19][Si:20]([C:23]([CH3:26])([CH3:24])[CH3:25])([CH3:22])[CH3:21])[CH2:17]2)[CH:52]=[CH:51][N:50]=[CH:49]1

Participants

5

Reactant 3

HCID 795ImidazoleHCID 10796Cesium carbonateHCID 24805984HCID 24805984, compound

Product 1

HCID 68469741HCID 68469741, compoundYield 60.3%

Reagents, catalysts & solvents 1

HCID 80711,2-DimethoxyethaneSolvent

Conditions

Temperature
85 °C

Procedure

In a clean, dry reaction vial equipped with a stirring bar were placed O6-(benzotriazol-1-yl)-2′,3′-bis-O-(tert-butyldimethylsilyl)-2′-deoxyinosine (26) (59.8 mg, 0.100 mmol), Cs2CO3 (65.2 mg, 0.200 mmol) and imidazole (13.6 mg, 0.200 mmol). Dry DME (1.0 mL) was added and the reaction mixture was flushed with N2 and the mixture was allowed to stir at 85° C. for 4 h. The reaction mixture was concentrated and the residue was dissolved in EtOAc. The mixture was washed with water, dried over Na2SO4, and evaporated to dryness. Chromatographic purification (SiO2, elution with 50% EtOAc in hexanes) afforded 32.0 mg (60% yield) of the title compound as a clear gum. Rf (20% EtOAc in hexanes)=0.07. 1H NMR (500 MHz, CDCl3): δ 9.19 (s, 1H, Ar—H), 8.77 (s, 1H, Ar—H), 8.48 (s, 1H, Ar—H), 8.40 (s, 1H, Ar—H), 7.25 (s, 1H, Ar—H), 6.56 (t, 1H, H-1′, J=6.3), 4.64 (app q, 1H, H-3′, Japp˜4.2), 4.06 (m, 1H, H-4′), 3.90 (dd, 1H, J=11.2, 3.9), 3.80 (dd, 1H, H-5′, J=11.2, 2.9), 2.65 (app quint, 1H, H-2′, Japp˜6.3), 2.51 (m, 1H, H-2′), 0.92, 0.915 (2 s, 18H, tert-Bu), 0.11, 0.10 (2 s, 12H, SiCH3). 13C NMR (126 MHz, CDCl3): δ 153.0, 152.1, 145.6, 143.0, 137.7, 130.6, 122.9, 117.3, 88.1, 84.7, 71.7, 62.6, 41.5, 25.9, 25.7, 18.4, 18.0, −4.7, −4.8, −5.4, −5.5.

Workup

  1. customIn a clean, dry
  2. customreaction
  3. customvial equipped with a stirring bar
  4. customthe reaction mixture was flushed with N2
  5. concentrationThe reaction mixture was concentrated
  6. dissolutionthe residue was dissolved in EtOAc
  7. washThe mixture was washed with water
  8. dry with materialdried over Na2SO4
  9. customevaporated to dryness
  10. customChromatographic purification (SiO2, elution with 50% EtOAc in hexanes)

Sources & evidence

ORD record
ord-240e16fbfdcf48a597927fd303f90c6e
Source dataset
uspto-grants-2013_08
Patent number
US08501931B2

Reaction notes

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