Cesium carbonate → HCID 91084416, compound

HRID 1889600Notes

Reaction equation

HRID 1889600 reaction equation
[Si](O[C@@H]1[C@@H](CO[Si](C(C)(C)C)(C)C)O[C@@H](N2C3N=CN=C(OC)C=3N=C2)C1)([C:4](C)([CH3:6])[CH3:5])(C)C.N1([O:43][C:44]2[C:45]3[N:46]=[CH:47][N:48]([C:71]=3[N:72]=[CH:73][N:74]=2)[C@@H:49]2[O:70][C@H:60]([CH2:61][O:62][Si:63]([C:66]([CH3:69])([CH3:68])[CH3:67])([CH3:65])[CH3:64])[C@@H:51]([O:52][Si:53]([C:56]([CH3:59])([CH3:58])[CH3:57])([CH3:55])[CH3:54])[CH2:50]2)C2C=CC=CC=2N=N1.C([O-])([O-])=O.[Cs+].[Cs+]>CC(O)C>[Si:63]([O:62][C@@H:61]1[C@@H:60]([CH2:51][O:52][Si:53]([C:56]([CH3:57])([CH3:59])[CH3:58])([CH3:54])[CH3:55])[O:70][C@@H:49]([N:48]2[C:71]3[N:72]=[CH:73][N:74]=[C:44]([O:43][CH:4]([CH3:6])[CH3:5])[C:45]=3[N:46]=[CH:47]2)[CH2:50]1)([C:66]([CH3:67])([CH3:69])[CH3:68])([CH3:64])[CH3:65]

Participants

5

Reactant 3

HCID 10796Cesium carbonateHCID 24805984HCID 24805984, compoundHCID 91567551HCID 91567551, compound

Product 1

HCID 91084416HCID 91084416, compoundYield 84%

Reagents, catalysts & solvents 1

HCID 3776IsopropanolSolvent

Procedure

As described for the synthesis of 3′,5′-bis-O-(tert-butyldimethylsilyl)-O6-methyl-2′-deoxyinosine, the isopropyl derivative was prepared by a reaction between O6-(benzotriazol-1-yl)-3′,5′-bis-O-(tert-butyldimethylsilyl)-2′-deoxyinosine (26) (59.8 mg, 0.100 mmol) and 2-propanol (1 mL) in the presence of Cs2CO3 (65.2 mg, 0.200 mmol) over 10 h. Chromatographic purification (SiO2, elution with 20% EtOAc in hexanes) afforded 44.1 mg (84% yield) of the title compound as a clear gum. Rf (20% EtOAc in hexanes)=0.31. 1H NMR (500 MHz, CDCl3): δ 8.50 (s, 1H, Ar—H), 8.23 (s, 1H, Ar—H), 6.49 (t, 1H, H-1′, J=6.3), 5.67 (septet, 1H, —CH—, J=6.3), 4.61 (m, 1H, H-3′), 4.02 (m, 1H, H-4′), 3.87 (dd, 1H, H-5′, J=11.2, 3.9), 3.78 (dd, 1H, H-5′, J=10.7, 2.9), 2.63 (app quint, 1H, H-2′, Japp˜6.3), 2.44 (ddd, 1H, H-2′, J=13.2, 5.9, 3.9), 1.47 (d, 6H, CH3, J=6.5), 0.91 (s, 18H, tert-Bu), 0.10, 0.09 (2 s, 12H, SiCH3). 13C NMR (126 MHz, CDCl3): δ 160.5, 152.0, 151.5, 140.3, 122.0, 87.9, 84.4, 71.9, 71.2, 62.8, 41.4, 26.0, 25.7, 22.0, 18.4, 18.0, −4.7, −4.8, −5.4, −5.5. FAB HRMS calcd for C25H47N4O4Si2 (M++H) 523.3136. found 523.3130.

Workup

  1. customChromatographic purification (SiO2, elution with 20% EtOAc in hexanes)

Sources & evidence

ORD record
ord-614b47639ba045d9ae367ae29503dfbc
Source dataset
uspto-grants-2013_08
Patent number
US08501931B2

Reaction notes

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