Cesium carbonate → HCID 91092114, compound

HRID 1889605Notes

Reaction equation

HRID 1889605 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:41]3[N:40]=[CH:39][N:38]=[C:27]([O:28][C:29]4[CH:34]=[CH:33][C:32]([N+]([O-])=O)=[CH:31][CH:30]=4)[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=CC=2N=N1.C([O-])([O-])=O.[Cs+].[Cs+].O[C:90]1[CH:102]=[CH:101][C:100]2C3C(=CC=CC=3)[CH2:93][C:92]=2[CH:91]=1>COCCOC>[Si:16]([O:15][C@@H:14]1[C@@H:13]([CH2:9][O:8][Si:1]([C:4]([CH3:6])([CH3:7])[CH3:5])([CH3:3])[CH3:2])[O:12][C@@H:11]([N:23]2[C:41]3[N:40]=[CH:39][N:38]=[C:27]([O:28][C:29]4[CH:34]=[CH:33][C:32]5[C:100]6[C:92](=[CH:91][CH:90]=[CH:102][CH:101]=6)[CH2:93][C:31]=5[CH:30]=4)[C:26]=3[N:25]=[CH:24]2)[CH2:10]1)([C:19]([CH3:22])([CH3:21])[CH3:20])([CH3:18])[CH3:17]

Participants

6

Reactant 4

HCID 10796Cesium carbonateHCID 755472-HydroxyfluoreneHCID 24805984HCID 24805984, compoundHCID 91289782HCID 91289782, compound

Product 1

HCID 91092114HCID 91092114, compoundYield 87%

Reagents, catalysts & solvents 1

HCID 80711,2-DimethoxyethaneSolvent

Procedure

As described for the synthesis of 3′,5′-bis-O-(tert-butyldimethylsilyl)-O6-(4-nitrophenyl)-2′-deoxyinosine, this fluorenyl 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), Cs2CO3 (65.2 mg, 0.200 mmol) and 2-hydroxyfluorene (20.0 mg, 0.110 mmol) in dry DME (1.0 mL) at 85° C. for 1 h. Chromatographic purification (SiO2, elution with 20% EtOAc in hexanes) afforded 56.0 mg (87% yield) of the title compound as a clear, yellowish gum. Rf (20% EtOAc in hexanes)=0.31. 1H NMR (500 MHz, CDCl1): δ 8.52 (s, 1H, Ar—H), 8.41 (s, 1H, Ar—H), 7.83 (d, 1H, Ar—H, J=8.3), 7.77 (d, 1H, Ar—H, J=7.3), 7.53 (d, 1H, Ar—H, J=7.3), 7.45 (s, 1H, Ar—H), 7.37 (t, 1H, Ar—H, J=7.6), 7.29 (t, 1H, Ar—H, J=7.8), 6.55 (t, 1H, H-1′, J=6.4), 4.66 (m, 1H, H-3′), 4.05 (q, 1H, H-4′, J=3.4), 3.94 (s, 2H, CH2), 3.92 (dd, 1H, H-2′, J=11.2, 4.1), 3.81 (dd, 1H, H-2′, J=11.2, 2.9), 2.67 (app quint, 1H, H-2′, Japp˜6.3), 2.50 (ddd, 1H, H-2′, J=13.2, 6.0, 4.3), 0.94, 0.93 (2 s, 18H, tert-Bu), 0.12 (s, 12H, SiCH3). 13C NMR (126 MHz, CDCl1): δ 160.5, 152.5, 152.1, 151.6, 144.7, 143.3, 141.6, 141.1, 139.5, 126.8, 126.5, 124.9, 122.2, 120.5, 120.47, 119.7, 118.7, 88.1, 84.7, 71.9, 62.8, 41.5, 37.0, 25.9, 25.7, 18.4, 18.0, −4.7, −4.8, −5.4, −5.5. FAB HRMS calcd for C35H49N4O4Si2 (M++H) 645.3292. found 645.3303.

Workup

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

Sources & evidence

ORD record
ord-cb59a8b0228a4097adf3cc661f9afef3
Source dataset
uspto-grants-2013_08
Patent number
US08501931B2

Reaction notes

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