Cesium carbonate → HCID 90905534, compound

HRID 1889599Notes

Reaction equation

HRID 1889599 reaction equation
[Si:1]([O:8][C@@H:9]1[C@@H:13]([CH2:14][O:15][Si:16]([C:19]([CH3:22])([CH3:21])[CH3:20])([CH3:18])[CH3:17])[O:12][C@@H:11]([N:23]2[C:33]3[N:32]=[CH:31][N:30]=[C:27]([O:28][CH3:29])[C:26]=3[N:25]=[CH:24]2)[CH2:10]1)([C:4]([CH3:7])([CH3:6])[CH3:5])([CH3:3])[CH3:2].N1(OC2C3N=CN(C=3N=CN=2)[C@@H]2O[C@H](CO[Si](C(C)(C)C)(C)C)[C@@H](O[Si](C(C)(C)C)(C)C)C2)C2C=CC=C[C:37]=2N=N1.C([O-])([O-])=O.[Cs+].[Cs+]>CCO>[Si:1]([O:8][C@@H:9]1[C@@H:13]([CH2:14][O:15][Si:16]([C:19]([CH3:20])([CH3:21])[CH3:22])([CH3:18])[CH3:17])[O:12][C@@H:11]([N:23]2[C:33]3[N:32]=[CH:31][N:30]=[C:27]([O:28][CH2:29][CH3:37])[C:26]=3[N:25]=[CH:24]2)[CH2:10]1)([C:4]([CH3:6])([CH3:7])[CH3:5])([CH3:3])[CH3:2]

Participants

5

Reactant 3

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

Product 1

HCID 90905534HCID 90905534, compoundYield 95%

Reagents, catalysts & solvents 1

HCID 702EthanolSolvent

Procedure

As described for the synthesis of 3′,5′-bis-O-(tert-butyldimethylsilyl)-O6-methyl-2′-deoxyinosine, the ethyl 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 EtOH (1 mL) in the presence of Cs2CO3 (65.2 mg, 0.200 mmol) over 1 h. Chromatographic purification (SiO2, elution with 20% EtOAc in hexanes) afforded 48.2 mg (95% yield) of the title compound as a clear gum. Rf (20% EtOAc in hexanes)=0.16. 1H NMR (500 MHz, CDCl3): δ 8.50 (s, 1H, Ar—H), 8.26 (s, 1H, Ar—H), 6.50 (t, 1H, H-1′, J=6.4), 4.65 (q, 2H, OCH2, J=7.0), 4.61 (m, 1H, H-3′), 4.01 (q, 1H, H-4′, J=3.4), 3.87 (dd, 1H, H-5′, J=11.2, 3.9), 3.77 (dd, 1H, H-5′, J=11.2, 2.9), 2.61 (quint, 1H, H-2′, J=6.3), 2.44 (ddd, 1H, H-2′, J=12.9, 6.1, 3.9), 1.50 (t, 3H, CH3, J=7.3), 0.91 (s, 18H, tert-Bu), 0.09, 0.08 (2 s, 12H, SiCH3). 13C NMR (126 MHz, CDCl3): δ 160.8, 152.0, 151.5, 140.5, 121.9, 87.9, 84.4, 71.8, 63.1, 62.7, 41.5, 26.0, 25.7, 18.4, 18.0, 14.5, −4.7, −4.8, −5.4, −5.5. FAB HRMS calcd for C24H45N4O4Si2 (M++H) 509.2979. found 509.2953.

Workup

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

Sources & evidence

ORD record
ord-554f08c6328e46799a1f4a887053333a
Source dataset
uspto-grants-2013_08
Patent number
US08501931B2

Reaction notes

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