Cesium carbonate → HCID 90687347, compound

HRID 1889603Notes

Reaction equation

HRID 1889603 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+:35]([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=C[C:45]=2N=N1.C(C1C=C(O)C=CC=1)#N.C([O-])([O-])=O.[Cs+].[Cs+]>COCCOC>[Si:16]([O:15][C@@H:14]1[C@@H:13]([CH2:9][O:8][Si:1]([C:4]([CH3:7])([CH3:5])[CH3:6])([CH3:2])[CH3:3])[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][CH:45]=[C:31]([C:32]#[N:35])[CH:30]=4)[C:26]=3[N:25]=[CH:24]2)[CH2:10]1)([C:19]([CH3:21])([CH3:22])[CH3:20])([CH3:18])[CH3:17]

Participants

6

Reactant 4

HCID 10796Cesium carbonateHCID 133943-CyanophenolHCID 24805984HCID 24805984, compoundHCID 91289782HCID 91289782, compound

Product 1

HCID 90687347HCID 90687347, compoundYield 82%

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 3-cyanophenyl 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 3-cyanophenol (13.1 mg, 0.110 mmol) in the presence of Cs2CO3 (65.2 mg, 0.200 mmol) in dry DME (1.0 mL) at 85° C. over 2 h. Chromatographic purification (SiO2, elution with 20% EtOAc in hexanes) afforded 47.5 mg (82% yield) of the title compound as a clear gum. Rf (50% EtOAc in hexanes)=0.58. 1H NMR (500 MHz, CDCl3): δ 8.49 (s, 1H, Ar—H), 8.45 (s, 1H, Ar—H), 7.62-7.54 (m, 4H, Ar—H), 6.54 (t, 1H, H-1′, J=6.4), 4.64 (m, 1H, H-3′), 4.05 (q, 1H, H-4′, J=3.4), 3.91 (dd, 1H, H-5′, J=11.2, 3.9), 3.80 (dd, 1H, H-5′, J=11.2, 3.9), 2.64 (app quint, 1H, H-2′, Japp˜6.3), 2.49 (ddd, 1H, H-2′, J=13.2, 6.3, 4.4), 0.92, 0.916 (2 s, 18H, tert-Bu), 0.11, 0.105 (2 s, 12H, SiCH3). 13C NMR (126 MHz, CDCl3): δ 159.1, 153.0, 152.7, 151.6, 142.2, 130.4, 129.2, 126.7, 125.6, 122.1, 117.9, 113.6, 88.1, 84.8, 71.8, 62.7, 41.5, 25.9, 25.7, 18.4, 17.9, −4.7, −4.8, −5.4, −5.5. FAB HRMS calcd for C29H44N5O4Si2 (M++H) 582.2932. found 582.2927.

Workup

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

Sources & evidence

ORD record
ord-94ab1a743cd84af0943796334f76cb53
Source dataset
uspto-grants-2013_08
Patent number
US08501931B2

Reaction notes

Loading…