Cesium carbonate → HCID 10673907, compound

HRID 576498Notes

Reaction equation

HRID 576498 reaction equation
[CH2:1]([O:4][C:5]1[C:6]2[N:7]=[CH:8][N:9]([C:40]=2[N:41]=[C:42]([NH2:44])[N:43]=1)[C@@H:10]1[O:39][C@H:29]([CH2:30][O:31][Si:32]([C:35]([CH3:38])([CH3:37])[CH3:36])([CH3:34])[CH3:33])[C@@H:20]([O:21][Si:22]([C:25]([CH3:28])([CH3:27])[CH3:26])([CH3:24])[CH3:23])[C@H:11]1O[Si](C(C)(C)C)(C)C)[CH:2]=[CH2:3].C([O-])([O-])=O.[Cs+].[Cs+]>C(O)C=C>[CH2:1]([O:4][C:5]1[C:6]2[N:7]=[CH:8][N:9]([C:40]=2[N:41]=[C:42]([NH2:44])[N:43]=1)[C@@H:10]1[O:39][C@H:29]([CH2:30][O:31][Si:32]([C:35]([CH3:36])([CH3:37])[CH3:38])([CH3:34])[CH3:33])[C@@H:20]([O:21][Si:22]([C:25]([CH3:28])([CH3:27])[CH3:26])([CH3:23])[CH3:24])[CH2:11]1)[CH:2]=[CH2:3]

Participants

4

Reactant 2

HCID 10796Cesium carbonateHCID 44186639HCID 44186639, compound

Product 1

HCID 10673907HCID 10673907, compoundYield 87%

Reagents, catalysts & solvents 1

HCID 7858Allyl AlcoholSolvent

Procedure

As described for the synthesis of 1a, this compound was prepared by a reaction of O6-(benzotriazol-1H-yl)-3′,5′-di-O-(tert-butyldimethylsilyl)-2′-deoxyguanosine25 (5.0 g, 8.16 mmol), allyl alcohol (50 mL) and Cs2CO3 (5.64 g, 17.1 mmol). Chromatographic purification of the crude material on a silica gel column using 30% EtOAc in hexanes) afforded 3.71 g (87% yield) of 1b as a white foam. Rf (SiO2/40% EtOAc in hexanes)=0.60. 1H NMR (CDCl3): δ 7.93 (s, 1H, Ar—H), 6.34 (t, 1H, H-1′, J=6.5 Hz), 6.17-6.09 (m, 1H, ═CH), 5.43 (dd, 1H, ═CHtrans, J=1.4, 17.2 Hz), 5.27 (dd, 1H, ═CHcis, J=1.4, 10.4 Hz), 5.01 (d, 2H, OCH2, J=5.7 Hz), 4.94 (s, 1H, NH2), 4.66-4.58 (m, 1H, H-3′), 3.99 (app q, 1H, H-4′, Japp˜3.5 Hz), 3.83 (dd, 1H, H-5′, J=4.4, 11.2 Hz), 3.77 (dd, 1H, H-5′, J=3.4, 11.2 Hz), 2.57 (app quint, 1H, H-2′, Japp˜6.5 Hz), 2.37 (ddd, 1H, H-2′, J=4.0, 6.0, 13.0 Hz), 0.92 (s, 18H, t-Bu), 0.11 and 0.09 (2s, 12H, SiCH3). 13C NMR (CDCl3): δ 160.0, 159.2, 153.5, 137.8, 132.8, 118.4, 116.0, 87.8, 88.8, 72.1, 67.5, 63.0, 41.1, 26.1, 25.9, 18.6, 18.1, −4.4, −4.6, −5.2, −5.3. HRMS calculated for C25H46N5O4Si2 [M+H]+: 536.3083. found: 536.3093.

Workup

  1. customChromatographic purification of the crude material on a silica gel column

Sources & evidence

ORD record
ord-bcc84e8560f5473baef35a760be5136e
Source dataset
uspto-grants-2015_05
Patent number
US09040498B2

Reaction notes

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