Morpholine → HCID 68468804, compound

HRID 1889607Notes

Reaction equation

HRID 1889607 reaction equation
N1(O[C:11]2[C:12]3[N:13]=[CH:14][N:15]([C:38]=3[N:39]=[CH:40][N:41]=2)[C@@H:16]2[O:37][C@H:27]([CH2:28][O:29][Si:30]([C:33]([CH3:36])([CH3:35])[CH3:34])([CH3:32])[CH3:31])[C@@H:18]([O:19][Si:20]([C:23]([CH3:26])([CH3:25])[CH3:24])([CH3:22])[CH3:21])[CH2:17]2)C2C=CC=CC=2N=N1.C([O-])([O-])=O.[Cs+].[Cs+].[NH:48]1[CH2:53][CH2:52][O:51][CH2:50][CH2:49]1>COCCOC>[N:48]1([C:11]2[N:41]=[CH:40][N:39]=[C:38]3[C:12]=2[N:13]=[CH:14][N:15]3[C@@H:16]2[O:37][C@H:27]([CH2:28][O:29][Si:30]([C:33]([CH3:36])([CH3:34])[CH3:35])([CH3:31])[CH3:32])[C@@H:18]([O:19][Si:20]([C:23]([CH3:24])([CH3:25])[CH3:26])([CH3:21])[CH3:22])[CH2:17]2)[CH2:53][CH2:52][O:51][CH2:50][CH2:49]1

Participants

5

Reactant 3

HCID 8083MorpholineHCID 10796Cesium carbonateHCID 24805984HCID 24805984, compound

Product 1

HCID 68468804HCID 68468804, compoundYield 78.2%

Reagents, catalysts & solvents 1

HCID 80711,2-DimethoxyethaneSolvent

Procedure

In a clean, dry reaction vial equipped with a stirring bar were placed 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 dry DME (1.0 mL). Morpholine (17.5 μL, 0.200 mmol) was added, the reaction mixture was flushed with N2, and the mixture was allowed to stir at room temperature for 1 h. The reaction mixture was concentrated and the residue was dissolved in EtOAc. The mixture was washed with 10% aq citric acid, sat aq NaHCO3 and brine. The organic layer was dried over Na2SO4 and evaporated to dryness. No additional purification was needed and 43 mg (78% yield) of the title compound was obtained. Rf (3% MeOH in CH2Cl2)=0.18. 1H NMR (500 MHz, CDCl3): δ 8.34 (s, 1H, Ar—H), 8.02 (s, 1H, Ar—H), 6.46 (t, 1H, H-1′, J=6.6), 4.59 (m, 1H, H-3′), 4.30 (br s, 4H, 2CH2), 4.01 (app q, 1H, H-4′, Japp˜3.4), 3.85-3.82 (m, 5H, H-5′ and 2CH2), 3.76 (dd, 1H, H-5′, J=11.0, 3.2), 2.59 (app quint, 1H, H-2′, Japp˜6.5), 2.42 (ddd, 1H, H-2′, J=13.2, 5.9, 3.9), 0.91 (s, 18H, tert-Bu), 0.09, 0.08, 0.076 (3 s, 12H, SiCH3). 13C NMR (126 MHz, CDCl3): δ 153.9, 152.3, 150.6, 136.8, 120.4, 87.8, 84.1, 72.0, 67.0, 62.8, 45.6, 41.1, 26.0, 25.7, 18.4, 18.0, −4.7, −4.8, −5.4, −5.5. FAB HRMS calcd for C26H48N5O4Si2 (M++H) 550.3245. found 550.3222.

Workup

  1. customIn a clean, dry
  2. customreaction
  3. customvial equipped with a stirring bar
  4. customthe reaction mixture was flushed with N2
  5. concentrationThe reaction mixture was concentrated
  6. dissolutionthe residue was dissolved in EtOAc
  7. washThe mixture was washed with 10% aq citric acid
  8. dry with materialThe organic layer was dried over Na2SO4
  9. customevaporated to dryness
  10. customNo additional purification

Sources & evidence

ORD record
ord-db8427745a6e4759a962444da5f3ae8a
Source dataset
uspto-grants-2013_08
Patent number
US08501931B2

Reaction notes

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