4-O-benzyl-N-benzyloxycarbonyl-1,5-imino-1,2,5-trideoxy-D-arabino-hexitol → Fagomine

HRID 2050672

Reaktionsgleichung

Reaktionsgleichung von HRID 2050672
C([O:8][C@@H:9]1[C@@H:14]([CH2:15][OH:16])[N:13](C(OCC2C=CC=CC=2)=O)[CH2:12][CH2:11][C@H:10]1[OH:27])C1C=CC=CC=1>C(O)(=O)C.[Pd]>[NH:13]1[C@H:14]([CH2:15][OH:16])[C@@H:9]([OH:8])[C@H:10]([OH:27])[CH2:11][CH2:12]1

Komponenten

4

Edukt 1

HCID 145234464-O-benzyl-N-benzyloxycarbonyl-1,5-imino-1,2,5-trideoxy-D-arabino-hexitol

Produkt 1

HCID 72259Fagomine

Reagenzien, Katalysatoren, Lösungsmittel 2

HCID 23938PalladiumKatalysatorHCID 176Acetic AcidLösungsmittel

Versuchsvorschrift

4-O-Benzyl-N-benzyloxycarbonyl-1,5-imino-1,2,5-trideoxy-D-arabino-hexitol (25) (325 mg, 0.877 mmol) was dissolved in acetic acid (8 ml) and stirred under hydrogen at atmospheric pressure with palladium black (100 mg). After 18 hours, the solution was filtered and evaporated. Subsequent purification by flash chromatography (CMAW) and ion exchange gave 1,5-imino-1,2,5-trideoxy-D-arabino-hexitol as the hydrochloride salt (158 mg, 98%) a white crystalline solid, m.p. (methanol-ether) 173°-175° C., [α]20D +17.9° (c, 0.78 in water); νmax (KBr disc) 3370, 1615, 1390, 1055, 935 and 660 cm-1 ; 1H NMR (D2O) δ 1.58 (1H, dddd, H-2, J2,2' 14.2 Hz, J2,3 11.4 Hz, J2,1 13.6 Hz, J2,1' 4.6 Hz); 2.06 (1H, dddd, J2',1' 2.4 Hz, J2',3 4.8 Hz, J2',1 3.2 Hz); 2.90-3.01 (2H, m, H-5, H-1); 3.30 (1H, ddd, H-1', J1,1' 13.2 Hz); 3.38 (1H, dd, H-4, J3,4 9.2 Hz, J4,5 10.5 Hz); 3.57 (1H, ddd, H-3); 3.73, 3.79 (2H, 2×dd, H-6,6', J6,6' 12.7 Hz, J5,6 5.2 Hz, J5,6' 3.4 Hz). 13C NMR δ29.33 (t, C-2); 42.66 (t, C-1); 58.53 (t, C-6); 60.68 (d, C-5); 70.39, 71.24 (2×d, C-3, C-4). m/z: 148 (M+H+, 100%), 116 (10%), 72 (8%). Also characterized as free base, m.p. (acetone-water) 178°-180° C., [lit.20 180°-184° C.], [α]20D +21.0° (c 0.3 in water) [lit.20 +24.7 (c 0.4 in water)]; 1H NMR δ 1.28 (1H, dddd, H-2), 1.81 (1H, dddd, H-2'), 2.40 (1H, ddd, H-1), 2.83 (1 H, ddd, H-1'), 2.99 (1H, dd, H-4), 3.37 (1H, m, H-3), 3.46 (1H, dd, H-6), 3.68 (1H, dd, H-6'); 13C NMR δ 33.45 (t, C-2), 43.30 (t, C-1), 61.59 (d, C-5), 62.45 (t, C-6), 73.98 (2×d, C-3,4).

Aufarbeitung

  1. filtrationthe solution was filtered
  2. customevaporated
  3. customSubsequent purification by flash chromatography (CMAW) and ion exchange

Quellen und Nachweise

ORD-Eintrag
ord-4bbf98bb34f54aaab887dbf992bf9c28
Quelldatensatz
uspto-grants-1991_05
Patentnummer
US05013842

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