Diisopropylethylamine → HCID 24805984, Verbindung

HRID 1889595Notizen

Reaktionsgleichung

Reaktionsgleichung von HRID 1889595
[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:32]3[N:31]=[CH:30][N:29]=[C:27]([OH:28])[C:26]=3[N:25]=[CH:24]2)[CH2:10]1)([C:4]([CH3:7])([CH3:6])[CH3:5])([CH3:3])[CH3:2].F[P-](F)(F)(F)(F)F.[N:40]1(O[P+](N(C)C)(N(C)C)N(C)C)[C:44]2[CH:45]=[CH:46][CH:47]=[CH:48][C:43]=2[N:42]=[N:41]1.CCN(C(C)C)C(C)C>C1COCC1>[N:40]1([O:28][C:27]2[C:26]3[N:25]=[CH:24][N:23]([C:32]=3[N:31]=[CH:30][N:29]=2)[C@@H:11]2[O:12][C@H:13]([CH2:14][O:15][Si:16]([C:19]([CH3:20])([CH3:21])[CH3:22])([CH3:17])[CH3:18])[C@@H:9]([O:8][Si:1]([C:4]([CH3:6])([CH3:7])[CH3:5])([CH3:3])[CH3:2])[CH2:10]2)[C:44]2[CH:45]=[CH:46][CH:47]=[CH:48][C:43]=2[N:42]=[N:41]1

Komponenten

5

Edukt 3

HCID 81531DiisopropylethylamineHCID 151348Benzotriazol-1-yloxy-tris(dimethylamino)phosphonium hexafluorophosphateHCID 178455234HCID 178455234, Verbindung

Produkt 1

HCID 24805984HCID 24805984, VerbindungAusbeute 83,1 %

Reagenzien, Katalysatoren, Lösungsmittel 1

HCID 8028TetrahydrofuranLösungsmittel

Versuchsvorschrift

In a 50 mL round-bottomed flask equipped with a stirring bar were placed 3′,5′-bis-O-(tert-butyldimethylsilyl)-2′-deoxyinosine (22) (1.005 g, 2.090 mmol) and BOP (1.850 g, 4.181 mmol). THF (20 mL) and DIPEA (0.55 mL, 3.135 mmol) were added and the mixture was allowed stir at room temperature for 23 h. The mixture was evaporated and CH2Cl2 (50 mL) added. The mixture was washed with water, dried over Na2SO4 and concentrated. Chromatographic purification (SiO2, elution with 20% EtOAc in hexanes) afforded 1.038 g (83% yield) of compound 26 as a white foam. Rf (20% EtOAc in hexanes)=0.14. 1H NMR (500 MHz, CDCl3): δ 8.54 (s, 1H, Ar—H), 8.41 (s, 1H, Ar—H), 8.14 (d, 1H, Ar—H, J=8.3), 7.55-7.41 (m, 3H, Ar—H), 6.55 (t, 1H, H-1′, J=6.1), 4.65 (m, 1H, H-3′), 4.06 (q, 1H, H-4′, J=3.1), 3.92 (dd, 1H, H-5′, J=11.2, 3.9), 3.80 (dd, 1H, H-5′, J=11.2, 2.7), 2.65 (app quint, 1H, H-2′, Japp˜6.3), 2.52 (m, 1H, H-2′), 0.93, 0.92 (2 s, 18H, tert-Bu), 0.11 (s, 12H, SiCH3). 13C NMR (126 MHz, CDCl3): δ 159.0, 153.6, 151.3, 143.5, 128.9, 128.7, 124.8, 120.6, 120.0, 108.6, 88.2, 85.0, 71.6, 62.6, 41.7, 25.9, 25.7, 18.4, 18.0, −4.7, −4.8, −5.4, −5.5. FAB HRMS calcd for C28H44N7O4Si2 (M++H) 598.2993. found 598.2986.

Aufarbeitung

  1. customIn a 50 mL round-bottomed flask equipped with a stirring bar
  2. customThe mixture was evaporated
  3. additionCH2Cl2 (50 mL) added
  4. washThe mixture was washed with water
  5. dry with materialdried over Na2SO4
  6. concentrationconcentrated
  7. customChromatographic purification (SiO2, elution with 20% EtOAc in hexanes)

Quellen und Nachweise

ORD-Eintrag
ord-07fbc4bd7111458783c1eacc200903bd
Quelldatensatz
uspto-grants-2013_08
Patentnummer
US08501931B2

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